CN106986332A - A kind of preparation method of flexible highly conductive graphene film - Google Patents
A kind of preparation method of flexible highly conductive graphene film Download PDFInfo
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Abstract
A kind of preparation method of flexible highly conductive graphene film, belongs to graphene film field.The invention solves the problems that there is size by equipment limit in existing graphene sponge, the technical problem of flexible difference in practical application.The inventive method：First, graphene oxide dispersion is freezed into 10h~24h under the conditions of 50 DEG C~20 DEG C, is then freeze-dried 72h~100h, obtains graphene oxide sponge；2nd, graphene oxide sponge is reduced with hydrazine hydrate steam；Three then using inert gas as protection gas, heat treatment；4th, pressurized treatments, obtain graphene film.The inventive method technique is simply with low cost, and production efficiency is high, controllability is good, can prepare large scale sample, the need for disclosure satisfy that different engineerings, solves the present situation that conventional big size graphene sponge is restricted by experimental facilities；And the present invention has been prepared while having the graphene film that flexible, electric conductivity is high, compactness is high.
Description
Technical field
The invention belongs to graphene film field；Specifically related to a kind of preparation method of flexible highly conductive graphene film.
Background technology
Graphene only has one layer of carbon atom, and tightly packed into bi-dimensional cellular shape lattice structure, each carbon atom and phase
Adjacent three carbon atoms formation covalent bond.Each carbon atom has a s track and three p tracks, wherein s tracks in graphene
The three carbon atoms formation chemical bond adjacent with surrounding with two p tracks, the electrical conductivity to graphene is not contributed, and remaining
The one mutual hydridization of p tracks, forms valence band and conduction band, affects the electric property of graphene.This unique two-dimensional structure makes
Graphene has excellent mechanics, electrically and thermally performance.Transmission of the free electron on graphene is not susceptible to scattering, electronics
Mobility can reach 2 × 105Cm/Vs, is more than 100 times of electron mobility in silicon；Its electrical conductivity is up to 106S/m, is
Excellent conductive material at room temperature.Graphene modulus of elasticity is up to 1TPa, and fracture strength is 125GPa, and room temperature thermal conductivity is 5.3
× 103W/mK, specific surface area is 2630m2/g.Graphene also has excellent optical property, the visible ray of single-layer graphene
Absorptivity is only 2.3%.This two-dimentional graphene film shows excellent in addition to high conductivity and transmitance, also
Chemical stability and heat endurance, can as solar energy transparency electrode substitute.Graphene is in composite, catalysis material
The fields such as material, energy storage material, high function nanometer electronic device, gas sensor have sizable application value, also attract numerous
Scholar's expansion is deeply systematically studied graphene.
For these excellent properties of application, it is necessary to extensive synthesizing graphite alkene, and single-layer graphene is assembled into grand
See structure.Preparing the method for graphene at present includes simple mechanical stripping graphite crystal, metal surface epitaxial growth, chemistry stripping
Powdered graphite is peeled off from graphene oxide or liquid phase ultrasound.Wherein, the method for chemical stripping graphene oxide is because process letter
Single, easily large-scale production is widely used in assembling graphene macrostructure.Graphene uniform is dispersed in matrix material
It is a kind of important research direction for playing graphene excellent properties in material, such as metal, macromolecule, inorganic material.However, because
The presence of graphene big L/D ratio, each other strong π-π, graphene is difficult to be uniformly dispersed in polymeric matrix material.
Tsing-Hua University Miao Zhang etc. utilize improved Hummers legal systems under the conditions of relatively low oxidizing temperature
Standby graphene oxide sheet, stablized afterwards it is scattered in aqueous, it is closed afterwards in a reservoir, 70 DEG C of thermal reduction 36h
Uniform graphene oxide hydrogel is formed, graphene oxide film is prepared using the dry method of casting, electrical conductivity can reach
To 802 ± 29S/cm.Its material shows good flexibility Fig. 1 and shows its flexibility for preparing material.
It is a difficult point to prepare flexible highly conductive graphene film at present, and it is thin to prepare graphene using the dry method of casting
Film, although flexible, but compactness is poor, influences electric conductivity.This patent is proposed to be prepared using graphene sponge for the first time and caused
Close highly conductive fexible film.
The content of the invention
The invention solves the problems that, there is preparation process complexity, lack of homogeneity, material in existing graphene fexible film preparation method
Expect that electrical conductivity is low, compactness is low, flexible poor problem；There is provided a kind of new flexible highly conductive fine and close stone based on graphene sponge
The preparation method of black alkene film.Graphene oxide is assembled into three-dimensional porous structure by the present invention --- graphene oxide sponge, lead to
Cross after electronation and be heat-treated, flexible highly conductive fine and close graphene film is prepared in finally pressurization；So as to solve
The problem of graphene film has flexibility, compactness, high conductivity simultaneously.A kind of flexible highly conductive graphene film in the present invention
Preparation method carry out in the steps below：
Step 1: graphene oxide dispersion is freezed into 10h~24h under the conditions of -50 DEG C~-20 DEG C, then freeze dry
Dry 72h~100h, obtains graphene oxide sponge (brown color)；
Step 2: being reduced with hydrazine hydrate steam to graphene oxide sponge, (Dark grey, density is 6~22mg/cm3)；
Step 3: then using inert gas as protection gas, carried out under the conditions of 1000 DEG C~5000 DEG C heat treatment 0.5h~
2h (thickness 1mm~10mm, 0.01~0.08g/cm of density-3)；
Step 4: then vacuum be 10~400Pa, pressure be 30Mpa~500Mpa under the conditions of carry out pressurized treatments,
Keep pressure 1min, obtain graphene film (thickness is 20~50 microns).
Graphene oxide described in step one is prepared as follows：Natural flake graphite is added in nitration mixture,
20min~60min is stirred with 200r/min~700r/min rotating speeds, divides 5~8 20~30min of minor tick equivalent to add afterwards high
Potassium manganate strong oxidizer, then it is 35 DEG C~80 DEG C to adjust whipping temp and speed, 200r/min~800r/min, and it is placed in water
Constant temperature stirs 5h~18h in bath, is then added in frozen water, and it is 30% hydrogen peroxide to add mass fraction into frozen water,
Reaction system color is changed into glassy yellow from brownish red, obtains suspension, filters, and centrifuge washing obtains graphene oxide；
Wherein, the mass ratio of the volume of described nitration mixture and natural flake graphite is (10mL~300mL):1g；Described
The quality of potassium permanganate and the volume ratio of nitration mixture are (8g~100g):1L；The quality and hydrogen peroxide of described natural flake graphite
Volume ratio be 1g:(2mL~8mL)；
Nitration mixture be the sulfuric acid and mass fraction that mass fraction is 15%~98% be 15%~80% phosphoric acid according to (3~
7)：1 volume ratio is mixed.
Described centrifuge washing processing is carried out according to the following steps：Using centrifugal separator, and add deionized water from
The heart is rinsed 3~7 times, is then added 0.1mol/L~1mol/L hydrochloric acid solution centrifugal rinsing 3~7 times, is eventually adding ethanol
Centrifugal rinsing 3~7 times；
Graphene oxide dispersion is by (0.3mg~24mg) by graphene oxide deionized water in step one：1mL's
What proportioning was mixed.
It is freeze-dried in step one under the conditions of -50 DEG C~-10 DEG C.
It is specifically that 80wt% hydrazine hydrate aqueous solutions and graphene oxide sponge are placed in closed drier in step 2,
Drier places hydrazine hydrate solution below, and graphene oxide sponge is placed in top, is heated to 50 DEG C~100 DEG C and is steamed using hydrazine hydrate
Vapour obtains the graphene sponge of Dark grey to graphene oxide sponge reductase 12 h~5h.
Hydrazine reducing agent described in step 2 is hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine.
Inert gas described in step 3 is argon gas or nitrogen.
Flexible graphene film metal gloss prepared by the present invention.
The inventive method technique is simply with low cost, and production efficiency is high, controllability is good, can prepare large scale sample, energy
The need for enough meeting different engineerings, solve the present situation that conventional big size graphene sponge is restricted by experimental facilities；Present invention system
Standby graphene film is flexible, can arbitrarily bend, the problem of solving flexible difference in graphene sponge practical application.
The stability of the preparation technology of the inventive method, it is workable, can large-scale industrial production.
The present invention graphene oxide is assembled into three-dimensional porous structure --- graphene oxide sponge, by electronation it
It is heat-treated afterwards, flexible highly conductive fine and close graphene film is prepared in finally pressurization；It is same so as to solve graphene film
When have flexibility, compactness, high conductivity the problem of, electrical conductivity can reach 105S/m。
Brief description of the drawings
Fig. 1 is the Flexible graphene film photo of the preparations such as Tsing-Hua University Miao Zhang；
Fig. 2 is the graphene sponge prepared；
Fig. 3 is the photo for the Flexible graphene film prepared；
Fig. 4 is the section SEM pictures of graphene fexible film.
Embodiment
Embodiment one：Present embodiment is provided one kind and answered using graphene sponge and dimethyl silicone polymer
The method and step that conjunction prepares highly conductive flexible composite is as follows：
First, graphene oxide is prepared：40g natural flake graphites are added in nitration mixture, stirred, condition is 500r/min,
40min.Divide afterwards and add potassium permanganate (time interval is 20min) for 7 times per minor tick 20min equivalent, adjustment whipping temp and
Speed is 35 DEG C, 500r/min, and is placed in constant temperature stirring 5h in water-bath, and stirring mixture is added in frozen water afterwards, and
And the hydrogen peroxide that mass fraction is 30% is added into frozen water, suspension is obtained, is finally filtered, centrifuge washing obtains oxygen
Graphite alkene, every milliliter adds 24mg graphene oxides proportioning and adds deionized water to obtain dispersion liquid.
The quality of described potassium permanganate and the volume ratio of nitration mixture are 6g:1L；The quality of described natural flake graphite with
The volume ratio of hydrogen peroxide is 1g:2mL；
The phosphoric acid that the sulfuric acid and mass fraction that it is 50% by mass fraction that nitration mixture, which is, are 50% is by 3：1 volume ratio mixing and
Into；
Centrifuge washing processing is carried out according to the following steps：Using centrifugal separator, and add deionized water centrifugal rinsing 5
It is secondary, 0.2mol/L hydrochloric acid solution centrifugal rinsing 5 times is then added, ethanol centrifugal rinsing is eventually adding 5 times；
2nd, graphene oxide sponge is prepared：The graphene oxide dispersion that step one is obtained is poured into mould ,-
24h is freezed under the conditions of 20 DEG C, then 72h is freeze-dried under the conditions of 30 DEG C and obtains brown color graphene oxide sponge (see Fig. 2), it is thick
Spend for 4mm.
3rd, redox graphene sponge：Using 80wt% hydrazine hydrate aqueous solution redox graphene sponges, by two kinds
Reactant is placed in drier, and drier places hydrazine hydrate solution below, and top places graphene oxide sponge, is placed in baking oven
In, it is heated to 90 DEG C and reduction 3h, the graphene oxide sponge after reduction is carried out to graphene oxide sponge using hydrazine hydrate steam
See Fig. 2 for Dark grey, obtain density for 22mg/cm3Graphene sponge.
4th, heat-treated graphite alkene sponge：By the graphene sponge of preparation, carried out under the conditions of Ar does protection gas, 1900 DEG C
It is heat-treated 1h.
5th, pressurization graphite alkene sponge：The graphene sponge for being heat-treated end is put into mould, afterwards in 300Mpa,
Pressurized treatments are carried out under the conditions of 11Pa, thickness is obtained and sees Fig. 3 for 50 micron graphite alkene films.
The present embodiment is by the thickness of test sample it is observed that the thickness for the graphene film prepared is micro- for 30
Rice, is observed that significant change will not occur for graphene film by bending the repetitive process opened, specific as shown in Figure 3.
Flexible graphene film conductivity prepared by present embodiment is 1.3 × 105S/m。
As shown in Figure 4, under the conditions of 10 microns of scale, the space that graphene fexible film section is present seldom, is showed
Go out very high compactness extent.
Embodiment two：A kind of preparation method of flexible highly conductive graphene film is by following in present embodiment
What step was carried out：
First, graphene oxide is prepared：20g natural flake graphites are added in sulfuric acid and phosphoric acid mixture is made, stirring,
Condition is 500r/min, 40min.Divide afterwards 7 times and potassium permanganate, adjustment whipping temp and speed are added per minor tick 20min equivalent
Rate is 35 DEG C, 500r/min, and is placed in constant temperature stirring 5h in water-bath, and stirring mixture is added in frozen water afterwards, and
The hydrogen peroxide that mass fraction is 30% is added into frozen water, graphene suspension is obtained, finally enters graphene oxide suspension
Row is filtered, and centrifuge washing obtains graphene oxide, and 12mg/ml is diluted using deionized water.
The quality of described potassium permanganate and the volume ratio of nitration mixture are 6g:1L；The quality of described natural flake graphite with
The volume ratio of hydrogen peroxide is 1g:2mL；
The phosphoric acid that the sulfuric acid and mass fraction that it is 50% by mass fraction that nitration mixture, which is, are 50% is by 3：1 volume ratio mixing and
Into；
Centrifuge washing processing is carried out according to the following steps：Using centrifugal separator, and add deionized water centrifugal rinsing 5
It is secondary, 0.2mol/L hydrochloric acid solution centrifugal rinsing 5 times is then added, ethanol centrifugal rinsing is eventually adding 5 times；
2nd, graphene oxide sponge is prepared：Obtained graphene oxide dispersion is poured into mould, in -20 DEG C of bars
24h is freezed under part, then 72h is freeze-dried under the conditions of -30 DEG C and obtains the graphene oxide sponge that brown color thickness is 4mm.
3rd, redox graphene sponge：Using 80wt% hydrazine hydrate aqueous solution redox graphene sponges, by two kinds
Reactant is placed in closed reaction vessel, and interlayer is placed, and hydrazine hydrate solution is placed below, and graphene oxide sea is placed in top
Silk floss, is placed in baking oven, is heated to 90 DEG C and carries out reduction 3h, the oxidation after reduction to graphene oxide sponge using hydrazine hydrate steam
Graphene sponge is Dark grey 3, obtains density for 12mg/cm3Graphene sponge.
4th, heat-treated graphite alkene sponge：By the graphene sponge of preparation, carried out under the conditions of Ar does protection gas, 2000 DEG C
It is heat-treated 1h.
5th, pressurization graphite alkene sponge：The graphene sponge for being heat-treated end is put into mould, afterwards in 500Mpa,
Pressurized treatments are carried out under the conditions of 11Pa, graphene film is obtained, Fig. 3 is seen.
The present embodiment is by the thickness of test sample it is observed that the thickness for the graphene film prepared is micro- for 30
Rice, is observed that significant change will not occur for graphene film by bending the repetitive process opened.
Flexible graphene film conductivity prepared by present embodiment is 1.2 × 105S/m。
Claims (10)
1. a kind of preparation method of flexible highly conductive graphene film, it is characterised in that this method is carried out in the steps below：
Step 1: graphene oxide dispersion is freezed into 10h~24h under the conditions of -50 DEG C~-20 DEG C, 72h is then freeze-dried
~100h, obtains graphene oxide sponge；
Step 2: being reduced with hydrazine reducing agent steam to graphene oxide sponge；
Step 3: then carrying out heat treatment 0.5h~2h under the conditions of 1000 DEG C~5000 DEG C using inert gas as protection gas；
Step 4: being then 10~400Pa in vacuum, pressure keeps to carry out pressurized treatments under the conditions of 30Mpa~500Mpa
Pressure 1min, obtains graphene film.
2. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that step one institute
The graphene oxide stated is prepared as follows：Natural flake graphite is added in nitration mixture, with 200r/min~700r/
Min rotating speeds stir 20min~60min, then divide 5~8 times and add potassium permanganate every 20min equivalent, then adjust whipping temp
It is 35 DEG C~80 DEG C with speed, 200r/min~800r/min, and it is placed in constant temperature stirring 5h~18h, Ran Houjia in water-bath
The hydrogen peroxide that mass fraction is 30% is added into frozen water, and into frozen water, suspension is obtained, filters, centrifuge washing is obtained
Graphene oxide；
Wherein, the mass ratio of the volume of described nitration mixture and natural flake graphite is (10mL~300mL):1g；Described Gao Meng
The quality of sour potassium and the volume ratio of nitration mixture are (8g~100g):1L；The quality of described natural flake graphite and the body of hydrogen peroxide
Product is than being 1g:(2mL~8mL)；
Nitration mixture be the sulfuric acid and mass fraction that mass fraction is 15%~98% be 15%~80% phosphoric acid according to (3~7)：1
Volume ratio mix.
3. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that in step one
Graphene oxide dispersion is by (0.3~24) mg by graphene oxide deionized water：What 1mL proportioning was mixed.
4. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that in step one
Graphene oxide dispersion is by 0.8mg by graphene oxide deionized water：What 1mL proportioning was mixed.
5. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that in step one
Graphene oxide dispersion is freezed into 24h under the conditions of -20 DEG C.
6. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that in step one
It is freeze-dried under the conditions of -50 DEG C~-20 DEG C.
7. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that in step 2
Specifically 80wt% hydrazines reducing agent aqueous solution and graphene oxide sponge are placed in closed drier, hydrazine is placed below
Graphene oxide sponge is placed in reducing agent aqueous solution, top, is heated to 50 DEG C~100 DEG C using hydrazine reducing agent water vapour to oxygen
Graphite alkene sponge reductase 12 h~5h, obtains the graphene sponge of Dark grey.
8. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that in step 2
Described hydrazine reducing agent is hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine.
9. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that in step 3
Described inert gas is argon gas or nitrogen.
10. a kind of preparation method of flexible highly conductive graphene film according to claim 1, it is characterised in that step 5 exists
Vacuum is 11Pa, and pressure is progress vacuum pressed processing under the conditions of 300Mpa, keeps pressure 1min, obtains graphene film.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107758644A (en) * | 2017-10-13 | 2018-03-06 | 杭州高烯科技有限公司 | A kind of method that super-pressure thermal reduction prepares graphene film |
| CN108910865A (en) * | 2018-07-21 | 2018-11-30 | 哈尔滨工业大学 | A method of preparing graphene/graphene nanobelt mixed film |
| CN110255535A (en) * | 2019-06-14 | 2019-09-20 | 中国航发北京航空材料研究院 | A kind of preparation method of conductive graphene film |
| CN110342498A (en) * | 2019-07-08 | 2019-10-18 | 浙江大学 | A kind of graphene-based elastic structure and preparation method thereof |
| CN110775966A (en) * | 2019-11-21 | 2020-02-11 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
| CN114190947A (en) * | 2021-12-09 | 2022-03-18 | 上海交通大学 | Non-invasive electroencephalogram sensor based on flexible substrate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107758644A (en) * | 2017-10-13 | 2018-03-06 | 杭州高烯科技有限公司 | A kind of method that super-pressure thermal reduction prepares graphene film |
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| CN110342498A (en) * | 2019-07-08 | 2019-10-18 | 浙江大学 | A kind of graphene-based elastic structure and preparation method thereof |
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| CN114190947A (en) * | 2021-12-09 | 2022-03-18 | 上海交通大学 | Non-invasive electroencephalogram sensor based on flexible substrate and preparation method thereof |
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