CN106032272B - A kind of amido enhancing graphene film, nitrogen-doped graphene film and preparation method thereof - Google Patents
A kind of amido enhancing graphene film, nitrogen-doped graphene film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses amido enhancing graphene film and preparation method, the method comprising the steps of (1) is added to the mixture of graphene oxide solution, water-soluble amine cross-linking agent and water-soluble reducing agent in flat void reactor；Water-soluble amine cross-linking agent is one of ethylenediamine, propane diamine, butanediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, ammonia, polyallylamine and p-phenylenediamine or a variety of；Water-soluble reducing agent is one of ascorbic acid, sodium ascorbate, sodium citrate, hydroiodic acid, hydrobromic acid, sodium hydrogensulfite and vulcanized sodium or a variety of；(2) flat void reactor is heated at 60~95 DEG C；(3) the amido enhancing graphene hydrogel that (2) obtain is drying to obtain.The invention also discloses nitrogen-doped graphene films and preparation method thereof, are heat-treated to above-mentioned amido enhancing graphene film.Method of the invention is simple, mild condition, and obtained graphene film structure is uniform, and mechanical performance is excellent.
Description
Technical field
The present invention relates to a kind of amido enhancing graphene films, nitrogen-doped graphene film and preparation method thereof.
Background technique
Most basic structural unit of the graphene as all carbon materials, with real monoatomic layer thickness and stringent two
Structure is tieed up, there is very high mechanical strength, elasticity, thermal conductivity, electric conductivity and quantum hall effect etc..Since Britain in 2010
Scientist An Delie Jim (Andre Geim) and Ke Siteyanuowosainuo (Konstantin Novoselov) have found graphite
Alkene and since obtaining the Nobel Prize, graphene research reaches unprecedented research climax, it is more and more the study found that its
Energy storage, electricity device, catalysis and biomedicine special dimension there is huge application prospect.
Consider from practical application angle, it is undoubtedly very valuable that nano-graphene material is changed into macrostructure material
Research direction.Currently, the research and preparation for macroscopical graphene-structured material have had numerous studies, including macroscopic view three
Tie up graphene-based block gel rubber material and two-dimensional graphene membrane material.Two-dimensional membrane structure is made of several single-layer graphenes
Stratiform flexibility class paper material.With going deep into for graphene research, preparing the method for this graphene film at present, there are two main classes:
One kind is by forming a film to graphene oxide vacuum filtration or thermal evaporation, and then reduction obtains graphene film；One kind is to graphite
Alkene piece or redox graphene piece carry out vacuum filtration or thermal evaporation film forming.The restoring method master of first kind graphene oxide membrane
It to include the methods of electronation, electrochemical reduction and thermal reduction.And graphene film or reduction employed in the second class method
Graphene oxide sheet can be obtained by the methods of chemical vapor deposition, mechanical stripping graphite or reducing agent reduction.Direct-reduction
Graphene oxide membrane is the fairly simple method for preparing graphene film, by the way that graphene oxide to be filtered to or evaporated membrane formation process system
It is standby to obtain graphene oxide membrane, then realized by the methods of high temperature thermal reduction.But this process needs higher temperature
Degree, the atmosphere such as inert gas or reducing gas, and technical difficulty is big, higher cost.And directly select graphene or reduction-oxidation
Graphene is filtered as raw material or is evaporated film forming, to the dispersibility of graphene and redox graphene solution require compared with
Height, the reunion for being otherwise easy to appear graphene film or redox graphene piece causes to be difficult to filter or evaporate film forming, and filters
Membrane formation process is difficult to large area preparation, equally limits its application.Meanwhile being prepared using above-mentioned method in the prior art
The mechanical strength of graphene film is lower, limiting its application property.Therefore, in view of certain limitation existing for above-mentioned all kinds of methods and
Some performance deficiencies existing for existing graphene film, one kind is at low cost, simple process, preparation temperature is low, preparation condition is mild, energy
The graphene film and preparation method thereof of large scale preparation and high mechanical strength has to be developed.
Summary of the invention
Technical problem to be solved by the present invention lies in the preparation method temperature in order to overcome graphene film in the prior art
High, complex process and the low defect of graphene film mechanical strength obtained, provide a kind of amido enhancing graphene film, N doping
Graphene film and preparation method thereof.Preparation method of the invention is easy to operate, and mild condition, raw material cost is low；Utilize this hair
The amido enhancing graphene film and nitrogen-doped graphene membrane structure that bright method is prepared are uniform, and mechanical performance is excellent, Yi Gong
Energyization.
The present invention is to solve above-mentioned technical problem by the following technical programs:
The present invention provides a kind of preparation methods of amido enhancing graphene film comprising following step:
(1) mixture of graphene oxide solution, water-soluble amine cross-linking agent and water-soluble reducing agent is added to flat
In shape void reactor；The water-soluble amine cross-linking agent is ethylenediamine, propane diamine, butanediamine, diethylenetriamine, triethylene
One of tetramine, tetraethylenepentamine, ammonia, polyallylamine and p-phenylenediamine are a variety of；The water-soluble reducing agent is anti-
One of bad hematic acid, sodium ascorbate, sodium citrate, hydroiodic acid, hydrobromic acid, sodium hydrogensulfite and vulcanized sodium are a variety of；
(2) flat void reactor is heated, the reduction and assembling of graphene oxide are carried out, flat amido is obtained and increases
Strong graphene hydrogel；The temperature of the heating is 60~95 DEG C；
(3) the dry amido enhancing graphene hydrogel enhances graphene film to get amido.
In step (1), the graphene oxide solution is made by conventional method in that art, preferably by improved oxidation
It removes graphite method (i.e. Hummers method) to be made, be made more preferably by following step: 1. being pre-oxidized: by graphite, the concentrated sulfuric acid and nitre
Acid is poured into water, and is filtered, drying, obtains pre-oxidation graphite；2. thermal expansion: by step pre-oxidation graphite 1. at 400~900 DEG C
10~30s of lower thermal expansion obtains thermal expansion graphite oxide；3. by the thermal expansion graphite oxide of step 2. and the concentrated sulfuric acid, persulfuric acid
Potassium (K2S2O8) and the mixture of phosphorus pentoxide heated at 80~90 DEG C, water filtration washing is added, it is dry, pre-oxidized
Thermally expand graphite；4. the pre-oxidation thermal expansion graphite of step 3. is mixed at 0~5 DEG C with the concentrated sulfuric acid, potassium permanganate is added, instead
It answers, adds hydrogen peroxide, stand, centrifuge washing, water is added and stirs up to graphene oxide solution.The graphite is generally ability
The conventional use of crystalline flake graphite in domain, the preferably crystalline flake graphite of 500 micron diameters.
In step (1), in the mixture, the dosage of the graphene oxide is preferably 1~30mg/mL mixing
Object；The mass ratio of the graphene oxide and the water-soluble amine cross-linking agent is preferably (1:0.1)~(1:200)；It is described
The mass ratio of graphene oxide and the water-soluble reducing agent is preferably (1:0.5)~(1:800), more preferably for (1:1)~
(1:200)。
In step (1), the flat void reactor uses general flat hollow rectangular reactor according,
The internal diameter height of the flat void reactor preferably > 1mm, preferably > 5, internal diameter length to height ratio is preferable for internal diameter the ratio of width to height
Ground > 5.The material of the flat void reactor is preferably polypropylene plastics, polyurethane plastics or silica gel plastics.
It is described by graphene oxide solution, the mixing of water-soluble amine cross-linking agent and water-soluble reducing agent in step (1)
After object is added in flat void reactor, the flat void reactor can be sealed, can also be with open-ended, preferably
Ground is sealing.
In step (2), the temperature of the heating is preferably 70~95 DEG C, and the time of the heating is preferably
0.5~100 hour.
In step (3), the temperature of the drying is preferably 10~100 DEG C, and the time of the drying is preferably 2
~100 hours.
The present invention also provides one kind amidos as made from above-mentioned preparation method to enhance graphene film.
The thickness and area of amido enhancing graphene film of the invention are adjustable, can be by control reactor size size and anti-
Object concentration is answered to be adjusted.The thickness of the amido enhancing graphene film is preferably 200~650 μm, and area is preferably 35
~2600cm2.The conductivity of the amido enhancing graphene film is greater than 8S/cm, and breaking strength is greater than 250MPa.
The present invention also provides a kind of preparation methods of nitrogen-doped graphene film comprising following step: according to this field
Conventional method, to the amido enhancing graphene film be heat-treated to get.
Wherein, the heat treatment can carry out in the conventional equipment of this field, preferably carry out in Muffle furnace.Described
The temperature of heat treatment is preferably 300~800 DEG C, and the time of the heat treatment is preferably 2~3 hours.Through Overheating Treatment
Afterwards, the electric conductivity and intensity of the nitrogen-doped graphene film obtained get a promotion.
Wherein, the heat treatment is preferably heat-treated in an inert atmosphere, is more preferably vacuum in an inert atmosphere
Heat treatment.The inert atmosphere is preferably one of nitrogen, argon gas and helium or a variety of.The vacuum heat treatment
Vacuum degree is preferably less than 0.1MPa.
The present invention also provides one kind nitrogen-doped graphene film as made from above-mentioned preparation method.
The thickness and area of nitrogen-doped graphene film of the invention are adjustable, can pass through control reactor size size, reaction
Object concentration and heat treatment temperature are adjusted.The thickness of the nitrogen-doped graphene film is preferably 200~650 μm, area compared with
It goodly is 35~2600cm2.The conductivity of the nitrogen-doped graphene film is greater than 30S/cm, and breaking strength is greater than 350MPa.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
(1) preparation method of amido of the invention enhancing graphene film uses graphene oxide solution that can restore with a step straight
It connects to obtain graphene film, reaction temperature is low, and operation is succinct.
(2) raw material that the present invention utilizes are gone back for graphene oxide and the water-soluble amine cross-linking agent of low cost with water-soluble
Former agent, source is very extensive, at low cost.
(3) reactor that the present invention utilizes can be using plastic pipe PP (polypropylene) quad flat hollow tube, and source is non-
Often extensively, at low cost, flexible, easy processing is reusable.
(4) different area size can be prepared using method of the invention, fracture tensile strength is 250~380MPa
Amido enhancing graphene film and nitrogen-doped graphene film, and gained amido enhancing graphene film appearance and consistent internal structure,
Satisfactory mechanical property, intensity is high, and flexible, flexibility is good, and conductivity is high, is greater than 8S/cm；Gained nitrogen-doped graphene film
Electric conductivity and intensity are increased dramatically, and conductivity is greater than 30S/cm, and breaking strength is greater than 350MPa.
(5) area of method of the invention is prepared amido enhancing graphene film and nitrogen-doped graphene film, thickness,
Pore size is easy through reactor size and reactant concentration and heat treatment temperature control in density and film.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
It is raw materials used commercially available in following embodiments.The film thickness and membrane area of graphene film pass through scanning electron
Microscope, vernier caliper and ruler measure, and film breaking strength is measured by omnipotent testing experiment machine, and conductivity is visited by four electrodes
The skill of handling needles measures.
Embodiment 1
A kind of amido enhancing graphene film, preparation method are as follows:
(1) the 1. preparation of graphene oxide solution:
500 micron diameter crystalline flake graphite 10g, 98% sulfuric acid 150ml, nitric acid 30ml are added to room temperature in 500ml conical flask
Stirring for 24 hours, slowly pours into 1L water and solid is collected by filtration, and washs 3 times, 80 DEG C dry 4 hours.Repeat preoxidation process twice.
Pre-oxidation graphite after drying is put into 900 DEG C of thermal expansion 20s in batch-type furnace and obtains thermal expansion graphite oxide.In 500ml wide-mouth
By 5g thermal expansion graphite oxide and 300ml sulfuric acid, 5g K in conical flask2S2O8, 80 DEG C of heating 4 are small after the mixing of 7g phosphorus pentoxide
When, it is diluted with 2L water, filtration washing, obtains within air drying 3 days pre-oxidation thermal expansion graphite.Dry pre-oxidation is thermally expanded
Graphite mixes at 0~5 DEG C of low temperature with 200ml sulfuric acid, and 20g potassium permanganate is added, is slowly added into, 35 DEG C of stirring 1h add 2L water
Dilution stands the hydrogen peroxide of addition 10ml 30% after 1h, stands 2 days, outwells supernatant, centrifuge washing, gentle agitation is divided
Dissipate preferable graphene oxide solution.
2. by step 1. graphene oxide solution obtained, amine cross-linking agent ethylenediamine and water-soluble reducing agent ascorbic acid
It is mixed with to obtain 4mg/ml graphene oxide mixed solution, wherein the mass ratio of graphene oxide and ethylenediamine and ascorbic acid is
1:200:100。
3. 2. graphene oxide mixed solution that step is obtained injects the flat-shaped polypropylene of square flat (PP) plastic reactor
In (inner height 2.5mm, length 20cm, width 20cm), port is sealed.
(2) plastic reactor sealed is heated into 2h under the conditions of 95 DEG C, forms flat amido in plastic tube and increases
Strong graphene hydrogel.Amido enhancing graphene hydrogel appearance is continuous, and thickness is uniform.
(3) in convection oven, gained amido enhancing graphene hydrogel is 100 hours dry under the conditions of 10 DEG C, i.e.,
The amido for obtaining dry state enhances graphene film, area 36cm2, it is smooth that gained amido enhances graphene film close structure.Graphene
Lamella accumulation is fine and close, and there is obvious pleated structure in inside, and the amido enhancing graphene film of dry state is measured in tensile load test
Breaking strength is 250MPa, and conductivity is greater than 8S/cm.
Embodiment 2
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution, butanediamine mix (wherein graphene oxide, fourth two with the complex reducing agent that hydroiodic acid and hydrobromic acid form
The mass ratio of amine, hydroiodic acid and hydrobromic acid is infused for the graphene oxide mixed solution of the 1:50:50:50) 2mg/ml being prepared
Enter in the flat-shaped polypropylene of square flat (PP) plastic reactor (inner height 8mm, length 10cm, width 10cm), seals port；It will envelope
Good plastic tube heats 3h under the conditions of 90 DEG C；In convection oven, by gained amido enhancing graphene hydrogel in 30 DEG C of items
It is 72 hours dry under part.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 3
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
The multiple crosslinking agent and NaHSO of graphite alkene solution, propane diamine and triethylene tetramine composition3Mix (wherein graphene oxide, third
Diamines, triethylene tetramine and NaHSO3Mass ratio be 1:0.1:0.5:100) graphene oxide of 30mg/ml that is prepared
Mixed solution injects in the flat-shaped polypropylene of square flat (PP) plastic reactor (inner height 1mm, length 10cm, width 10cm), envelope
Good port；The plastic tube sealed is heated into 4h under the conditions of 80 DEG C；In convection oven, gained amido is enhanced into graphene water-setting
Glue is 60 hours dry under the conditions of 50 DEG C.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 4
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution, diethylenetriamine mix (wherein graphite oxide with the complex reducing agent that ascorbic acid and sodium citrate form
Alkene, diethylenetriamine, ascorbic acid and sodium citrate mass ratio be 1:10:10:50) the oxidation stone of 6mg/ml that is prepared
In the black alkene mixed liquor injection flat-shaped polypropylene of square flat (PP) plastic reactor (inner height 6mm, length 10cm, width 10cm),
Port is sealed, is reacted for 24 hours under the conditions of 75 DEG C；In convection oven, by gained amido enhancing graphene hydrogel in 70 DEG C of items
It is 24 hours dry under part.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 5
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution, p-phenylenediamine and ammonia composition multiple crosslinking agent mixed with sodium ascorbate (wherein graphene oxide, to benzene
The mass ratio of diamines, ammonia and sodium ascorbate is 1:0.5:10:10) graphene oxide liquid mixture of 15mg/ml that is prepared
It injects in the flat-shaped polypropylene of square flat (PP) plastic reactor (inner height 5.5mm, length 50cm, width 50cm), seals port；
It is in convection oven, gained amido enhancing graphene hydrogel is 10 hours dry under the conditions of 90 DEG C.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 6
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution, polyallylamine and Na2S mixes (wherein graphene oxide, polyallylamine and Na2The mass ratio of S is 1:
The graphene oxide liquid mixture for 6mg/ml 0.1:200) being prepared injects the flat-shaped polypropylene of square flat (PP) plastic reactor
In (inner height 4mm, length 50cm, width 50cm), port is sealed；The plastic tube sealed is heated into 96h under the conditions of 70 DEG C；?
It is in convection oven, gained amido enhancing graphene hydrogel is 2 hours dry under the conditions of 95 DEG C.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 7
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution, tetraethylenepentamine and ascorbic acid mix (the wherein matter of graphene oxide, tetraethylenepentamine and ascorbic acid
Amount is injected the flat-shaped polypropylene of square flat (PP) than the graphene oxide liquid mixture for the 1.5mg/ml being prepared for 1:0.1:800)
In plastic reactor (inner height 8mm, length 100cm, width 100cm), port is sealed；By the plastic tube sealed in 95 DEG C of conditions
Lower heating 0.5h.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 8
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution, ethylenediamine and ascorbic acid mixing (mass ratio of graphene oxide, ethylenediamine and ascorbic acid be 1:100:
0.5) graphene oxide liquid mixture for the 2mg/ml being prepared, the injection flat-shaped polypropylene of square flat (PP) plastic reactor are (interior
Height 4mm, length 100cm, width 100cm) in, seal port.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 9
A kind of amido enhancing graphene film, preparation method are as follows:
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution, tetraethylenepentamine and hydrobromic acid and Na2The complex reducing agent of S composition mixes (wherein, graphene oxide, four
Five amine of ethylene, hydrobromic acid and Na2The mass ratio of S is 1:50:25:25) graphene oxide liquid mixture of 2mg/ml that is prepared
It injects in the flat-shaped polypropylene of square flat (PP) plastic reactor (inner height 18mm, length 50cm, width 50cm), seals port.
The conductivity of obtained amido enhancing graphene film is greater than 8S/cm, film thickness, area and tensile strength such as table 1
It is shown.
Embodiment 10
A kind of nitrogen-doped graphene film, preparation method are as follows:
The enhancing graphene film sample of dry state amido made from embodiment 1 is put into muffle furnace, 500 DEG C are passed through nitrogen, then
Heat treatment 2h is vacuumized to get nitrogen-doped graphene film.The conductivity of gained nitrogen-doped graphene film is greater than 30S/cm, film thickness
Degree, area and tensile strength are as shown in table 1.
Embodiment 11
A kind of nitrogen-doped graphene film, preparation method are as follows:
The enhancing graphene film sample of dry state amido made from embodiment 1 is put into muffle furnace, 300 DEG C are passed through nitrogen, then
Heat treatment 3h is vacuumized to get nitrogen-doped graphene film.The conductivity of gained nitrogen-doped graphene film is greater than 30S/cm, film thickness
Degree, area and tensile strength are as shown in table 1.
Embodiment 12
A kind of nitrogen-doped graphene film, preparation method are as follows:
The enhancing graphene film sample of dry state amido made from embodiment 1 is put into muffle furnace, 800 DEG C are passed through nitrogen, then
Heat treatment 2h is vacuumized to get nitrogen-doped graphene film.The conductivity of gained nitrogen-doped graphene film is greater than 30S/cm, film thickness
Degree, area and tensile strength are as shown in table 1.
Comparative example 1
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution and water-soluble reducing agent hydrazine hydrate (NH2-NH2(H2O the graphene oxide liquid mixture)) being mixed with, injection
It is sealed in the flat-shaped PP plastic reactor of square flat (inner height 4mm, length 10cm, width 10cm), wherein graphene oxide and water
The mass ratio of soluble reducing agent is 1:100.What its result obtained is the graphene particles being deposited in pipe, cannot be continuous wet
State graphene film equally also cannot get continuous dry graphene film.
Comparative example 2
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution injects sealing in the flat-shaped PP plastic reactor of square flat (inner height 6mm, length 10cm, width 10cm),
Middle reaction temperature is 95 DEG C, reaction time 2h.As a result, cannot get continuous hygrometric state graphene film, it also cannot be continuous
Dry graphene film.
Comparative example 3
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution injects open-ended in the flat-shaped PP plastic reactor of square flat (inner height 4mm, length 10cm, width 10cm),
Wherein reaction temperature is 95 DEG C, reaction time 2h.As a result, cannot get continuous hygrometric state graphene film, it also cannot be continuous
Dry graphene film.
Comparative example 4
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution and sodium ascorbate are mixed with to obtain graphene oxide liquid mixture, and not plus amine cross-linking agent, injection are rectangular
Flat polypropylene (PP) plastic reactor seals port.
The conductivity of obtained graphene film is greater than 8S/cm, and film thickness, area and tensile strength are as shown in table 1.It draws
Intensity is stretched to be substantially reduced.
Comparative example 5
It is carried out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are all the same: by pure oxygen
Graphite alkene solution mixes (wherein the mass ratio of graphene oxide and diethylenetriamine is 1:10) with diethylenetriamine and is prepared into
The graphene oxide liquid mixture of the 6mg/ml arrived, the injection flat-shaped polypropylene of square flat (PP) plastic reactor seal port.
The conductivity of obtained amido enhancing graphene film is about 0.1S/cm, because its conductance of water-soluble reducing agent is not added
Performance is substantially reduced.Its film thickness, area and tensile strength are as shown in table 1.
The average thickness and breaking strength data of the graphene film of 1 embodiment 1~12 of table and comparative example 1~5
Claims (12)
1. a kind of preparation method of amido enhancing graphene film, which is characterized in that it includes the following steps:
(1) mixture of graphene oxide solution, water-soluble amine cross-linking agent and water-soluble reducing agent is added in flat
In empty reactor；The water-soluble amine cross-linking agent is propane diamine, butanediamine, diethylenetriamine, triethylene tetramine, four ethylene
One of five amine, ammonia and polyallylamine are a variety of；The water-soluble reducing agent is ascorbic acid, sodium ascorbate, lemon
One of lemon acid sodium, hydroiodic acid, hydrobromic acid, sodium hydrogensulfite and vulcanized sodium are a variety of；
In the mixture, the mass ratio of the graphene oxide and the water-soluble amine cross-linking agent be (1:0.1)~(1:
200)；
In the mixture, the mass ratio of the graphene oxide and the water-soluble reducing agent be (1:0.5)~(1:
800)；
(2) flat void reactor is heated, the reduction and assembling of graphene oxide are carried out, obtains flat amido enhancing stone
Black alkene hydrogel；The temperature of the heating is 60~95 DEG C；
(3) the dry amido enhancing graphene hydrogel enhances graphene film to get amido.
2. preparation method as described in claim 1, which is characterized in that in step (1), in the mixture, the oxidation
The dosage of graphene is 1~30mg/mL mixture.
3. preparation method as described in claim 1, which is characterized in that in step (1), in the mixture, the oxidation
The mass ratio of graphene and the water-soluble reducing agent is (1:1)~(1:200).
4. preparation method as described in claim 1, which is characterized in that in step (1), the flat void reactor
Internal diameter height > 1mm, internal diameter the ratio of width to height > 5, internal diameter length to height ratio > 5；
And/or in step (1), the material of the flat void reactor is polypropylene plastics, polyurethane plastics or silica gel
Plastics；
It is described by the mixed of graphene oxide solution, water-soluble amine cross-linking agent and water-soluble reducing agent and/or in step (1)
After conjunction object is added in flat void reactor, the flat void reactor is sealed；
And/or in step (1), the graphene oxide solution is made by following step: 1. being pre-oxidized: by graphite, dense sulphur
Acid and nitric acid are poured into water, and are filtered, drying, obtain pre-oxidation graphite；2. thermal expansion: by step pre-oxidation graphite 1. 400
10~30s is thermally expanded at~900 DEG C, obtains thermal expansion graphite oxide；3. by the thermal expansion graphite oxide of step 2. and the concentrated sulfuric acid,
The mixture of potassium peroxydisulfate and phosphorus pentoxide heats at 80~90 DEG C, and water filtration washing is added, dry, obtains pre-oxidation heat
Expanded graphite；4. the pre-oxidation thermal expansion graphite of step 3. is mixed at 0~5 DEG C with the concentrated sulfuric acid, potassium permanganate is added, instead
It answers, adds hydrogen peroxide, stand, centrifuge washing, water is added and stirs up to graphene oxide solution.
5. preparation method as described in claim 1, which is characterized in that in step (2), the temperature of the heating is 70~95
DEG C, the time of the heating is 0.5~100 hour；
And/or in step (3), the temperature of the drying is 10~100 DEG C, and the time of the drying is 2~100 hours.
6. a kind of preparation method of amido enhancing graphene film, which is characterized in that it includes the following steps:
(1) mixture of graphene oxide solution, p-phenylenediamine, ammonia and sodium ascorbate is added to flat void reactor
In；The graphene oxide solution, p-phenylenediamine, ammonia and sodium ascorbate mass ratio be 1:0.5:10:10；
(2) flat void reactor is heated, the reduction and assembling of graphene oxide are carried out, obtains flat amido enhancing stone
Black alkene hydrogel；The temperature of the heating is 90 DEG C；
(3) the dry amido enhancing graphene hydrogel enhances graphene film to get amido.
7. a kind of preparation method of amido enhancing graphene film, which is characterized in that it includes the following steps:
(1) mixture of graphene oxide solution, ethylenediamine and ascorbic acid is added in flat void reactor；It is described
Graphene oxide solution, ethylenediamine and ascorbic acid mass ratio be 1:100:0.5；
(2) flat void reactor is heated, the reduction and assembling of graphene oxide are carried out, obtains flat amido enhancing stone
Black alkene hydrogel；The temperature of the heating is 95 DEG C；
(3) the dry amido enhancing graphene hydrogel enhances graphene film to get amido.
8. amido made from a kind of preparation method as described in any one of claim 1~7 enhances graphene film.
9. a kind of preparation method of nitrogen-doped graphene film, which is characterized in that it includes the following steps: to described in claim 8
Amido enhancing graphene film be heat-treated to get.
10. preparation method as claimed in claim 9, which is characterized in that the temperature of the heat treatment is 300~800 DEG C, institute
The time for the heat treatment stated is 2~3 hours；
And/or the heat treatment is to be heat-treated in an inert atmosphere, the inert atmosphere is in nitrogen, argon gas and helium
It is one or more.
11. preparation method as claimed in claim 10, which is characterized in that the heat treatment is Vacuum Heat in an inert atmosphere
Processing；The vacuum degree of the vacuum heat treatment is less than 0.1MPa.
12. nitrogen-doped graphene film made from a kind of preparation method as described in claim 10 or 11.
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