CN106032272A - An amino-enhanced graphene membrane, a nitrogen-doped graphene membrane and preparing methods thereof - Google Patents
An amino-enhanced graphene membrane, a nitrogen-doped graphene membrane and preparing methods thereof Download PDFInfo
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Abstract
An amino-enhanced graphene membrane and a preparing method thereof are disclosed. The method includes (1) adding a mixture of a graphene oxide solution, a water-soluble amine type crosslinking agent and a water-soluble reductant into a flat-shape hollow reactor, with the water-soluble amine type crosslinking agent being one or more selected from a group consisting of ethylenediamine, diaminopropane, diaminobutane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ammonia, poly(allylamine) and para-phenylene diamine, and the water-soluble reductant being one or more selected from a group consisting of ascorbic acid, sodium ascorbate, sodium citrate, hydroiodic acid, hydrobromic acid, sodium hydrogen sulfite and sodium sulfide, (2) heating the reactor at 60-95 DEG C, and (3) drying amino-enhanced graphene hydrogel prepared in the step (2). A nitrogen-doped graphene membrane and a preparing method thereof are also disclosed. The nitrogen-doped graphene membrane is prepared by subjecting the amino-enhanced graphene membrane to heat processing. The methods are simple and mild in conditions, and the prepared graphene membranes are uniform in structure and excellent in mechanical properties.
Description
Technical field
The present invention relates to a kind of amido and strengthen graphene film, nitrogen-doped graphene film and preparation method thereof.
Background technology
Graphene as the most basic construction unit of all material with carbon elements, have real monoatomic layer thickness and
Strict two-dimensional structure, has the highest mechanical strength, elasticity, heat conductivity, electric conductivity and quantum suddenly
Your effect etc..Since British scientist An Delie Jim (Andre Geim) in 2010 and Ke Siteya
Since Nuo Wosainuo (Konstantin Novoselov) finds that Graphene obtains Nobel Prize, Graphene
Research reaches unprecedented research climax, more and more studies discovery, and it is in energy storage, electricity
Device, catalysis and biomedical special dimension have huge application prospect.
Consider from reality application angle, nano-graphene material is changed into macrostructure material right and wrong undoubtedly
Normal valuable research direction.At present, research and preparation for macroscopic view graphene-structured material have had
Numerous studies, including macroscopic three dimensional graphene-based block gel rubber material and two-dimensional graphene membrane material.Two
The stratiform flexibility class paper material that the membrane structure of dimension is made up of some single-layer graphenes.Along with Graphene grinds
That studies carefully gos deep into, and the method preparing this graphene film at present mainly has two classes: a class is by oxidation stone
Ink alkene vacuum filtration or thermal evaporation film forming, then reduction obtains graphene film；One class be to graphene film or
Redox graphene sheet carries out vacuum filtration or thermal evaporation film forming.The reduction of first kind graphene oxide membrane
Method mainly includes the methods such as electronation, electrochemical reduction and thermal reduction.And Equations of The Second Kind method is adopted
Graphene film or redox graphene sheet can by chemical gaseous phase deposit, mechanical stripping graphite or
The methods such as reducing agent reduction obtain.Direct-reduction graphene oxide membrane is fairly simple to prepare graphene film
Method, by by graphene oxide sucking filtration or flash to embrane method and prepare graphene oxide membrane, then
Realize through methods such as high-temperature hot reduction.But this process needs higher temperature, noble gas
Or the atmosphere such as reducing gas, and technical difficulty is big, relatively costly.And directly select Graphene or oxygen reduction
Functionalized graphene carries out sucking filtration or evaporation film forming as raw material, to Graphene and redox graphene solution
Dispersibility requires higher, the most easily occurs that the reunion of graphene film or redox graphene sheet causes difficulty
With sucking filtration or evaporation film forming, and sucking filtration membrane formation process is difficult to large area and prepares, and limits its application equally.With
Time, the mechanical strength using the graphene film that above-mentioned method of the prior art prepares is relatively low, limits
Its application.Therefore, the certain limitation and the existing graphene film that exist in view of above-mentioned all kinds of methods are deposited
Some performance deficiencies, a kind of low cost, simple process, preparation temperature is low, preparation condition is gentle,
Can prepare on a large scale and graphene film that mechanical strength is high and preparation method thereof has to be developed.
Summary of the invention
The technical problem to be solved is to overcome the preparation of graphene film in prior art
The defect that method temperature height, complex process and prepared graphene film mechanical strength are low, it is provided that a kind of amine
Base strengthens graphene film, nitrogen-doped graphene film and preparation method thereof.The preparation method operation letter of the present invention
Single, mild condition, the cost of raw material is low；The amido utilizing the method for the present invention to prepare strengthens graphite
Alkene film and nitrogen-doped graphene membrane structure are uniform, and mechanical performance is excellent, easy functionalization.
The present invention is to solve above-mentioned technical problem by the following technical programs:
The invention provides a kind of amido and strengthen the preparation method of graphene film, it comprises the steps:
(1) by graphene oxide solution, water solublity amine cross-linking agent and the mixture of water-soluble reducing agent
Join in flat void reactor；Described water solublity amine cross-linking agent be ethylenediamine, propane diamine,
Butanediamine, diethylenetriamine, triethylene tetramine, TEPA, ammonia, PAH and to benzene two
One or more in amine；Described water-soluble reducing agent is ascorbic acid, sodium ascorbate, citric acid
One or more in sodium, hydroiodic acid, hydrobromic acid, sodium sulfite and sodium sulfide；
(2) heating flat void reactor, carries out reduction and the assembling of graphene oxide, obtains flat
Flat-shaped amido strengthens Graphene hydrogel；The temperature of described heating is 60～95 DEG C；
(3) it is dried described amido and strengthens Graphene hydrogel, obtain amido and strengthen graphene film.
In step (1), described graphene oxide solution is prepared by this area conventional method, preferably
Peeled off graphite method (i.e. Hummers method) by the oxidation improved to prepare, more preferably by following step system
: 1. pre-oxidation: graphite, concentrated sulphuric acid and nitric acid are poured into water, filter, dry, pre-oxidized
Graphite；2. thermal expansion: by step pre-oxidation graphite thermal expansion 10～30s at 400～900 DEG C 1.,
To thermal expansion graphite oxide；3. by step thermal expansion graphite oxide 2. and concentrated sulphuric acid, potassium peroxydisulfate
(K2S2O8) and the mixture of phosphorus pentoxide heat at 80～90 DEG C, add water filtration washing, dry
Dry, obtain pre-oxidizing thermal expansion graphite；4. by step pre-oxidation thermal expansion graphite 3. with concentrated sulphuric acid at 0～5 DEG C
Lower mixing, adds potassium permanganate, reaction, adds hydrogen peroxide, stand, centrifuge washing, adds water and stirs
Mix and i.e. obtain graphene oxide solution.Described graphite is generally crystalline flake graphite commonly used in the art, preferably
Ground is the crystalline flake graphite of 500 micron diameters.
In step (1), in described mixture, the consumption of described graphene oxide is preferably
1～30mg/mL mixture；Described graphene oxide is preferable with the mass ratio of described water solublity amine cross-linking agent
Ground is (1:0.1)～(1:200)；The mass ratio of described graphene oxide and described water-soluble reducing agent is relatively
It is (1:0.5)～(1:800) goodly, is more preferably (1:1)～(1:200).
In step (1), described flat void reactor uses general flat hollow cuboid
Reactor, the internal diameter height of described flat void reactor is preferably > 1mm, internal diameter width is high
Ratio is preferably > 5, internal diameter length to height ratio is preferably > 5.The material of described flat void reactor is preferably
For polypropylene plastics, polyurethane plastics or silica gel plastics.
In step (1), described by graphene oxide solution, water solublity amine cross-linking agent and water solublity
After the mixture of reducing agent joins in flat void reactor, described flat void reactor can
With sealing, it is also possible to open-ended, preferably sealing.
In step (2), the temperature of described heating is preferably 70～95 DEG C, the time of described heating
Preferably 0.5～100 hour.
In step (3), the described temperature being dried is preferably 10～100 DEG C, described be dried time
Between preferably 2～100 hours.
Present invention also offers a kind of amido prepared by above-mentioned preparation method and strengthen graphene film.
Thickness and the area of the amido enhancing graphene film of the present invention are adjustable, can be by controlling reactor size
Size and reactant concentration are adjusted.Described amido strengthens the thickness of graphene film preferably
200～650 μm, area is preferably 35～2600cm2.The conductivity that described amido strengthens graphene film is big
In 8S/cm, fracture strength is more than 250MPa.
Present invention also offers the preparation method of a kind of nitrogen-doped graphene film, its comprise the steps: by
According to this area conventional method, described amido is strengthened graphene film and carries out heat treatment, to obtain final product.
Wherein, described heat treatment can be carried out in the conventional equipment of this area, preferably enters in Muffle furnace
OK.The temperature of described heat treatment is preferably 300～800 DEG C, and the time of described heat treatment is preferably
It it is 2～3 hours.After Overheating Treatment, electric conductivity and the intensity of the nitrogen-doped graphene film obtained are carried
Rise.
Wherein, described heat treatment heat treatment the most in an inert atmosphere, is more preferably at indifferent gas
Vacuum heat in atmosphere.Described inert atmosphere is preferably the one in nitrogen, argon and helium or many
Kind.The vacuum of described vacuum heat is preferably less than 0.1MPa.
The present invention also provides for a kind of nitrogen-doped graphene film prepared by above-mentioned preparation method.
Thickness and the area of the nitrogen-doped graphene film of the present invention are adjustable, can be big by controlling reactor size
Little, reactant concentration and heat treatment temperature are adjusted.The thickness of described nitrogen-doped graphene film is preferably
Being 200～650 μm, area is preferably 35～2600cm2.The conductivity of described nitrogen-doped graphene film
More than 30S/cm, fracture strength is more than 350MPa.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can combination in any, i.e. get Ben Fa
Bright each preferred embodiments.
Agents useful for same of the present invention and raw material are the most commercially.
The most progressive effect of the present invention is:
(1) preparation method of the amido enhancing graphene film of the present invention uses graphene oxide solution permissible
One step reduction directly obtains graphene film, and reaction temperature is low, and operation is succinct.
(2) the water solublity amine cross-linking agent that the raw material that the present invention utilizes is graphene oxide and low cost
And water-soluble reducing agent, originate widely, low cost.
(3) reactor that the present invention utilizes can use in plastic pipe PP (polypropylene) quad flat
Blank pipe, originates widely, and low cost is flexible, easily processes, repeatable utilization.
(4) method utilizing the present invention can prepare different area size, fracture tensile strength is
The amido of 250～380MPa strengthens graphene film and nitrogen-doped graphene film, and gained amido strengthens graphite
Alkene film appearance and consistent internal structure, satisfactory mechanical property, intensity is high, and flexible, pliability is good, electricity
Conductance is high, more than 8S/cm；Gained nitrogen-doped graphene film electric conductivity and intensity be increased dramatically,
Conductivity is more than 30S/cm, and fracture strength is more than 350MPa.
(5) method of the present invention prepares amido strengthens graphene film and nitrogen-doped graphene film
Area, thickness, density and film mesopore size easily by reactor size and reactant concentration and
Heat treatment temperature controls.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to often
Rule method and condition, or select according to catalogue.
In following embodiment, raw materials used the most commercially.Film thickness and the membrane area of graphene film pass through
Scanning electron microscope, slide gauge and ruler record, and film fracture strength is surveyed by omnipotent testing experiment machine
, conductivity is recorded by four electrode catheter methods.
Embodiment 1
A kind of amido strengthens graphene film, and its preparation method is as follows:
(1) preparation of 1. graphene oxide solution:
500 micron diameter crystalline flake graphite 10g, 98% sulphuric acid 150ml, nitric acid 30ml, join 500ml
24h is stirred at room temperature in conical flask, slowly pours into and solid in 1L water, is collected by filtration, wash 3 times, 80 DEG C
Dry 4 hours.Repeat preoxidation process twice.Dried pre-oxidation graphite is put in batch-type furnace 900 DEG C
Thermal expansion 20s obtains thermal expansion graphite oxide.5g thermal expansion is aoxidized by 500ml wide mouthed Erlenmeyer bottle
Graphite and 300ml sulphuric acid, 5g K2S2O8, latter 80 DEG C of 7g phosphorus pentoxide mixing is heated 4 hours, uses
2L water dilutes, filtration washing, and air drying obtains pre-oxidizing thermal expansion graphite for 3 days.By dry
Pre-oxidation thermal expansion graphite mixes at low temperature 0～5 DEG C with 200ml sulphuric acid, adds 20g potassium permanganate,
It is slowly added into, 35 DEG C of stirring 1h, adds the hydrogen peroxide adding 10ml 30% after the dilution of 2L water stands 1h,
Standing 2 days, outwell supernatant, centrifuge washing, gentle agitation obtains disperseing preferable graphene oxide molten
Liquid.
2. graphene oxide solution, amine cross-linking agent ethylenediamine and the water-soluble reducing agent 1. step prepared
Ascorbic acid is mixed with to obtain 4mg/ml graphene oxide mixed solution, wherein graphene oxide and second two
The mass ratio of amine and ascorbic acid is 1:200:100.
3. graphene oxide mixed solution step 2. obtained injects the flat-shaped polypropylene of square flat (PP) and moulds
In material reactor (inner height 2.5mm, length 20cm, width 20cm), seal port.
(2) the plastics reactor sealed is heated 2h under the conditions of 95 DEG C, formed flat in plastic tube
The amido of shape strengthens Graphene hydrogel.It is continuous that this amido strengthens Graphene hydrogel outward appearance, and thickness is uniform.
(3) in convection oven, gained amido is strengthened Graphene hydrogel and is dried under the conditions of 10 DEG C
100 hours, the amido obtaining dry state strengthened graphene film, and area is 36cm2, gained amido strengthens stone
Ink alkene membrane structure is the most smooth.Graphene sheet layer piles up densification, and there is obvious pleated structure inside, in stretching
The fracture strength of the amido enhancing graphene film measuring dry state in load test is 250MPa, and conductivity is big
In 8S/cm.
Embodiment 2
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
The complex reducing agent that pure graphene oxide solution, butanediamine form with hydroiodic acid and hydrobromic acid is mixed
Prepared by (wherein graphene oxide, butanediamine, hydroiodic acid and hydrobromic mass ratio are 1:50:50:50)
It is anti-that the graphene oxide mixed solution of the 2mg/ml obtained injects square flat flat-shaped polypropylene (PP) plastics
Answer in device (inner height 8mm, length 10cm, width 10cm), seal port；The plastics that will seal
Pipe heats 3h under the conditions of 90 DEG C；In convection oven, gained amido enhancing Graphene hydrogel is existed
It is dried 72 hours under the conditions of 30 DEG C.
The amido obtained strengthens the conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 3
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
By pure graphene oxide solution, propane diamine and triethylene tetramine form multiple crosslinking agent with
NaHSO3Mixing (wherein graphene oxide, propane diamine, triethylene tetramine and NaHSO3Mass ratio
For 1:0.1:0.5:100) the graphene oxide mixed solution of 30mg/ml for preparing injects quad flat
In shape polypropylene (PP) plastics reactor (inner height 1mm, length 10cm, width 10cm),
Seal port；The plastic tube sealed is heated 4h under the conditions of 80 DEG C；In convection oven, by gained
Amido strengthens Graphene hydrogel and is dried 60 hours under the conditions of 50 DEG C.
The amido obtained strengthens the electrical conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 4
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
Pure graphene oxide solution, diethylenetriamine are gone back with ascorbic acid and the compound of sodium citrate composition
(wherein the mass ratio of graphene oxide, diethylenetriamine, ascorbic acid and sodium citrate is in former dose of mixing
The graphene oxide liquid mixture of 6mg/ml 1:10:10:50) prepared injects the flat-shaped polypropylene of square flat
(PP), in plastics reactor (inner height 6mm, length 10cm, width 10cm), port is sealed,
24h is reacted under the conditions of 75 DEG C；In convection oven, gained amido is strengthened Graphene hydrogel at 70 DEG C
Under the conditions of be dried 24 hours.
The amido obtained strengthens the conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 5
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
The multiple crosslinking agent that pure graphene oxide solution, p-phenylenediamine and ammonia form is mixed with sodium ascorbate
Close (wherein the mass ratio of graphene oxide, p-phenylenediamine, ammonia and sodium ascorbate is 1:0.5:10:10)
The graphene oxide liquid mixture of the 15mg/ml prepared injects square flat flat-shaped polypropylene (PP) plastics
In reactor (inner height 5.5mm, length 50cm, width 50cm), seal port；Dry in air blast
In case, gained amido is strengthened Graphene hydrogel and is dried 10 hours under the conditions of 90 DEG C.
The amido obtained strengthens the conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 6
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
By pure graphene oxide solution, PAH and Na2S mixing (wherein graphene oxide, poly-
Allyl amine and Na2The mass ratio of S is 1:0.1:200) graphene oxide of 6mg/ml for preparing mixes
Conjunction liquid, injection square flat flat-shaped polypropylene (PP) plastics reactor (inner height 4mm, length 50cm,
Width 50cm) in, seal port；The plastic tube sealed is heated 96h under the conditions of 70 DEG C；Rousing
In wind baking oven, gained amido is strengthened Graphene hydrogel and is dried 2 hours under the conditions of 95 DEG C.
The amido obtained strengthens the conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 7
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
By pure graphene oxide solution, TEPA and ascorbic acid mix (wherein graphene oxide,
The mass ratio of TEPA and ascorbic acid is 1:0.1:800) oxidation of 1.5mg/ml for preparing
Graphene mixed liquor, injection square flat flat-shaped polypropylene (PP) plastics reactor (inner height 8mm,
Length 100cm, width 100cm) in, seal port；The plastic tube sealed is added under the conditions of 95 DEG C
Hot 0.5h.
The amido obtained strengthens the conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 8
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
By pure graphene oxide solution, ethylenediamine and ascorbic acid mix (graphene oxide, ethylenediamine and
The mass ratio of ascorbic acid is 1:100:0.5) graphene oxide liquid mixture of 2mg/ml for preparing,
Injection square flat flat-shaped polypropylene (PP) plastics reactor (inner height 4mm, length 100cm, wide
Degree 100cm) in, seal port.
The amido obtained strengthens the conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 9
A kind of amido strengthens graphene film, and its preparation method is as follows:
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
By pure graphene oxide solution, TEPA and hydrobromic acid and Na2The complex reducing agent of S composition
Mixing (wherein, graphene oxide, TEPA, hydrobromic acid and Na2The mass ratio of S is 1:50:25:25)
The graphene oxide liquid mixture of the 2mg/ml prepared injects square flat flat-shaped polypropylene (PP) plastics
In reactor (inner height 18mm, length 50cm, width 50cm), seal port.
The amido obtained strengthens the conductivity of graphene film more than 8S/cm, its film thickness, area and stretching
Intensity is as shown in table 1.
Embodiment 10
A kind of nitrogen-doped graphene film, its preparation method is as follows:
The dry state amido that embodiment 1 prepares being strengthened graphene film sample and puts into muffle furnace, 500 DEG C lead to
Enter nitrogen, then evacuation heat treatment 2h, obtain nitrogen-doped graphene film.Gained nitrogen-doped graphene film
Conductivity is more than 30S/cm, and its film thickness, area and hot strength are as shown in table 1.
Embodiment 11
A kind of nitrogen-doped graphene film, its preparation method is as follows:
The dry state amido that embodiment 1 prepares being strengthened graphene film sample and puts into muffle furnace, 300 DEG C lead to
Enter nitrogen, then evacuation heat treatment 3h, obtain nitrogen-doped graphene film.Gained nitrogen-doped graphene film
Conductivity is more than 30S/cm, and its film thickness, area and hot strength are as shown in table 1.
Embodiment 12
A kind of nitrogen-doped graphene film, its preparation method is as follows:
The dry state amido that embodiment 1 prepares being strengthened graphene film sample and puts into muffle furnace, 800 DEG C lead to
Enter nitrogen, then evacuation heat treatment 2h, obtain nitrogen-doped graphene film.Gained nitrogen-doped graphene film
Conductivity is more than 30S/cm, and its film thickness, area and hot strength are as shown in table 1.
Comparative example 1
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
By pure graphene oxide solution and water-soluble reducing agent hydrazine hydrate (NH2-NH2(H2O)) it is mixed with
Graphene oxide liquid mixture, inject square flat flat-shaped PP plastics reactor (inner height 4mm, length
10cm, width 10cm) middle sealing, wherein graphene oxide is 1:100 with the mass ratio of water-soluble reducing agent.
What its result obtained is the Graphene granule being deposited in pipe, can not get continuous print hygrometric state graphene film, with
Sample also can not get continuous print dry graphene film.
Comparative example 2
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
Pure graphene oxide solution is injected square flat flat-shaped PP plastics reactor (inner height 6mm, length
Degree 10cm, width 10cm) middle sealing, wherein reaction temperature is 95 DEG C, and the response time is 2h.Its
Result is to can not get continuous print hygrometric state graphene film, also can not get continuous print dry graphene film.
Comparative example 3
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
Pure graphene oxide solution is injected square flat flat-shaped PP plastics reactor (inner height 4mm, length
Degree 10cm, width 10cm) in open-ended, wherein reaction temperature is 95 DEG C, and the response time is 2h.
Its result is to can not get continuous print hygrometric state graphene film, also can not get continuous print dry graphene film.
Comparative example 4
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
Pure graphene oxide solution and sodium ascorbate are mixed with and obtain graphene oxide liquid mixture, not
Add amine cross-linking agent, inject square flat flat-shaped polypropylene (PP) plastics reactor and seal port.
The conductivity of the graphene film obtained is more than 8S/cm, its film thickness, area and hot strength such as table
Shown in 1.Its hot strength substantially reduces.
Comparative example 5
Carrying out according to the preparation method of embodiment 1, in addition to having following difference, other conditions are the most identical:
Pure graphene oxide solution is mixed with diethylenetriamine (wherein graphene oxide and diethylenetriamine
Mass ratio be 1:10) graphene oxide liquid mixture of 6mg/ml for preparing, inject quad flat
Shape polypropylene (PP) plastics reactor seals port.
The amido obtained strengthens the conductivity of graphene film and is about 0.1S/cm, because not adding water solublity reduction
Its conductivity of agent substantially reduces.Its film thickness, area and hot strength are as shown in table 1.
Table 1 embodiment 1～12 and the average thickness of graphene film of comparative example 1～5 and fracture strength data
Claims (10)
1. the preparation method of an amido enhancing graphene film, it is characterised in that it comprises the steps:
(1) by graphene oxide solution, water solublity amine cross-linking agent and the mixture of water-soluble reducing agent
Join in flat void reactor；Described water solublity amine cross-linking agent be ethylenediamine, propane diamine,
Butanediamine, diethylenetriamine, triethylene tetramine, TEPA, ammonia, PAH and to benzene two
One or more in amine；Described water-soluble reducing agent is ascorbic acid, sodium ascorbate, citric acid
One or more in sodium, hydroiodic acid, hydrobromic acid, sodium sulfite and sodium sulfide；
(2) heating flat void reactor, carries out reduction and the assembling of graphene oxide, obtains flat
Flat-shaped amido strengthens Graphene hydrogel；The temperature of described heating is 60～95 DEG C；
(3) it is dried described amido and strengthens Graphene hydrogel, obtain amido and strengthen graphene film.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), described
In mixture, the consumption of described graphene oxide is 1～30mg/mL mixture；
And/or, in step (1), in described mixture, described graphene oxide and described water solublity
The mass ratio of amine cross-linking agent is (1:0.1)～(1:200)；
And/or, in step (1), in described mixture, described graphene oxide and described water solublity
The mass ratio of reducing agent is (1:0.5)～(1:800).
3. preparation method as claimed in claim 2, it is characterised in that in step (1), described
In mixture, described graphene oxide is (1:1)～(1:200) with the mass ratio of described water-soluble reducing agent.
4. preparation method as claimed in claim 1, it is characterised in that in step (1), described
The internal diameter height of flat void reactor > 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 described flat void reactor be polypropylene plastics,
Polyurethane plastics or silica gel plastics；
And/or, in step (1), described by graphene oxide solution, water solublity amine cross-linking agent and
After the mixture of water-soluble reducing agent joins in flat void reactor, to described flat hollow
Reactor seals；
And/or, in step (1), described graphene oxide solution is prepared by following step: the most pre-
Oxidation: graphite, concentrated sulphuric acid and nitric acid are poured into water, filters, and dries, and obtains pre-oxidizing graphite；②
Thermal expansion: by step pre-oxidation graphite thermal expansion 10～30s at 400～900 DEG C 1., obtain thermal expansion
Graphite oxide；3. by step thermal expansion graphite oxide 2. and concentrated sulphuric acid, potassium peroxydisulfate and phosphorus pentoxide
Mixture heat at 80～90 DEG C, add water filtration washing, be dried, obtain pre-oxidize thermal expansion stone
Ink；4. step pre-oxidation thermal expansion graphite 3. is mixed with concentrated sulphuric acid at 0～5 DEG C, add permanganic acid
Potassium, reaction, add hydrogen peroxide, stand, centrifuge washing, add water and stir that i.e. to obtain graphene oxide molten
Liquid.
5. preparation method as claimed in claim 1, it is characterised in that in step (2), described
The temperature of heating is 70～95 DEG C, and the time of described heating is 0.5～100 hour；
And/or, in step (3), the described temperature being dried is 10～100 DEG C, described be dried time
Between be 2～100 hours.
6. the amido enhancing graphene film that a preparation method as described in any one of Claims 1 to 5 prepares.
7. the preparation method of a nitrogen-doped graphene film, it is characterised in that it comprises the steps:
Amido described in claim 6 is strengthened graphene film and carries out heat treatment, to obtain final product.
8. preparation method as claimed in claim 7, it is characterised in that the temperature of described heat treatment
Being 300～800 DEG C, the time of described heat treatment is 2～3 hours；
And/or, described heat treatment is heat treatment in an inert atmosphere, described inert atmosphere be nitrogen,
One or more in argon and helium.
9. preparation method as claimed in claim 8, it is characterised in that described heat treatment is lazy
Vacuum heat in property atmosphere；The vacuum of described vacuum heat is less than 0.1MPa.
10. the nitrogen-doped graphene film that a preparation method as described in claim 8 or 9 prepares.
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| CN201510109892.3A CN106032272B (en) | 2015-03-13 | 2015-03-13 | A kind of amido enhancing graphene film, nitrogen-doped graphene film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106494028A (en) * | 2016-12-28 | 2017-03-15 | 镇江博昊科技有限公司 | A kind of flexible multi-layered graphene composite film and preparation method thereof |
| CN107236165A (en) * | 2017-07-13 | 2017-10-10 | 上海通茗检测技术服务有限公司 | A kind of preparation method of rubber/graphene composite material with isolation structure |
| CN107651668A (en) * | 2017-09-07 | 2018-02-02 | 山东大学 | A kind of expansible preparation method of the grapheme material of high density N doping |
| CN109294519A (en) * | 2018-11-17 | 2019-02-01 | 哈尔滨烯创科技有限公司 | A kind of preparation method of the wideband graphene absorbing material of multilayered structure concentration gradient design |
| CN114212778A (en) * | 2021-12-29 | 2022-03-22 | 杭州嘉悦智能设备有限公司 | Preparation method of nitrogen-doped graphene film and nitrogen-doped graphene film |
| CN114348997A (en) * | 2021-12-29 | 2022-04-15 | 杭州嘉悦智能设备有限公司 | Nitrogen-doped graphene-metal nanoparticle film and preparation method thereof |
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| CN103265012A (en) * | 2013-04-26 | 2013-08-28 | 华中科技大学 | Methods for preparing large-area graphene film and large-area graphene composite films |
| CN103966699A (en) * | 2014-01-14 | 2014-08-06 | 中国科学院上海应用物理研究所 | Preparation method of graphene fibers |
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| CN103265012A (en) * | 2013-04-26 | 2013-08-28 | 华中科技大学 | Methods for preparing large-area graphene film and large-area graphene composite films |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106494028A (en) * | 2016-12-28 | 2017-03-15 | 镇江博昊科技有限公司 | A kind of flexible multi-layered graphene composite film and preparation method thereof |
| CN107236165A (en) * | 2017-07-13 | 2017-10-10 | 上海通茗检测技术服务有限公司 | A kind of preparation method of rubber/graphene composite material with isolation structure |
| CN107236165B (en) * | 2017-07-13 | 2019-02-26 | 上海通茗检测技术服务有限公司 | A kind of rubber/graphene composite material preparation method with isolation structure |
| CN107651668A (en) * | 2017-09-07 | 2018-02-02 | 山东大学 | A kind of expansible preparation method of the grapheme material of high density N doping |
| CN107651668B (en) * | 2017-09-07 | 2020-04-07 | 山东大学 | Extensible preparation method of high-density N-doped graphene material |
| CN109294519A (en) * | 2018-11-17 | 2019-02-01 | 哈尔滨烯创科技有限公司 | A kind of preparation method of the wideband graphene absorbing material of multilayered structure concentration gradient design |
| CN109294519B (en) * | 2018-11-17 | 2021-06-25 | 哈尔滨烯创科技有限公司 | Preparation method of broadband graphene wave-absorbing material with multilayer structure concentration gradient design |
| CN114212778A (en) * | 2021-12-29 | 2022-03-22 | 杭州嘉悦智能设备有限公司 | Preparation method of nitrogen-doped graphene film and nitrogen-doped graphene film |
| CN114348997A (en) * | 2021-12-29 | 2022-04-15 | 杭州嘉悦智能设备有限公司 | Nitrogen-doped graphene-metal nanoparticle film and preparation method thereof |
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