CN104163420B - Ag doping Graphene extrusion coating paper and preparation method thereof - Google Patents
Ag doping Graphene extrusion coating paper and preparation method thereof Download PDFInfo
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- CN104163420B CN104163420B CN201410361337.5A CN201410361337A CN104163420B CN 104163420 B CN104163420 B CN 104163420B CN 201410361337 A CN201410361337 A CN 201410361337A CN 104163420 B CN104163420 B CN 104163420B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Abstract
The present invention relates to a kind of Ag doping Graphene extrusion coating paper and preparation method thereof.The preparation method of Ag doping Graphene extrusion coating paper includes preparing graphene oxide, described graphene oxide is carried out supersound process, prepares graphene oxide suspension；In described graphene oxide suspension, add silver nitrate obtain mixed liquor；It is evaporated described mixed liquor processing, obtains Ag doping graphene oxide composite paper；And described Ag doping graphene oxide composite paper put into the solution containing reducing agent carries out reduction treatment, obtain the step of Ag doping Graphene extrusion coating paper.The method is relative to vacuum filtration method, and reaction condition is gentle, and low for equipment requirements, technique is simple.Further, our experiments show that, the thermal conductivity of the vertical direction of preparation-obtained Ag doping Graphene extrusion coating paper is higher.
Description
Technical field
The present invention relates to electronic package material field, particularly relate to Ag doping Graphene extrusion coating paper and preparation thereof
Method.
Background technology
Along with electronic device develops to computing field highly integrated, high, heat radiation becomes a difficult problem.All the time,
The traditional heat-dissipating material such as copper, silver is widely used in electronic device and product heat radiation.But copper, ag material valency
Lattice are expensive, the most oxidized, and density is high, and thermal coefficient of expansion is big, and material with carbon element due to high heat conduction, low-density,
Low thermal coefficient of expansion and rich reserves, a series of excellent specific properties such as cheap and gradually rise.Research shows
The heat conductivity of common CNT is 3000～3500W/m K, and diamond is 1000～2200W/m K, and
The heat conductivity of single-layer graphene is more up to 5300W/m K.
Graphene is the new material of monolayer atomic building, and its carbon atom is with sp2Hybrid orbital composition hexagonal Nidus Vespae is brilliant
Lattice.All the time, Graphene is considered as hypothetical structure, it is impossible to individually stable existence.2004,
Univ Manchester UK physicist Andre Geim and Konstantin Novoselov utilizes adhesive tape from stone
Repeatedly glue lower thin slice on ink, finally have successfully been isolated out Graphene.Graphene due to its special physical arrangement,
There is a series of excellent specific property: the thinnest, the hardest nano material, the most fully transparent, only
Absorb the light of 2.3%；Heat conductivity is up to 5300 W/m K, higher than CNT and diamond；Under room temperature its
Electron mobility is more than 15000cm2/ V s, again than CNT or silicon wafer height；And resistivity about 10-6
Ω cm is lower than copper or silver, for the material that world resistivity is minimum.Chinese Academy of Sciences's Shanxi coal chemistry grinds
Study carefully Kong Qingqiang etc. utilize vacuum filtration that chopped carbon fiber and graphene oxide are prepared as extrusion coating paper, then lead to
Crossing high-temperature thermal annealing and obtain Graphene extrusion coating paper, the thermal conductivity in its horizontal plane is up to 977W/mK, but hangs down
Nogata to thermal conductivity only have 0.38W/mK.And the product area of vacuum filtration acquisition is little, high-temperature thermal annealing
Power consumption is big, is not suitable for industrialized production, needs to find a kind of simple method, it is achieved large-scale production,
And the pyroconductivity of the product vertical direction obtained to have lifting by a relatively large margin.
Summary of the invention
Based on this, it is necessary to provide a kind of technique simple Ag doping Graphene extrusion coating paper, to prepare Vertical Square
To the higher Ag doping Graphene extrusion coating paper of thermal conductivity.
Further, it is provided that a kind of silver prepared by the preparation method of above-mentioned Ag doping Graphene extrusion coating paper is mixed
Miscellaneous Graphene extrusion coating paper.
The preparation method of a kind of Ag doping Graphene extrusion coating paper, comprises the steps:
Prepare graphene oxide, described graphene oxide is carried out supersound process, prepares graphene oxide
Suspension；
In described graphene oxide suspension, add silver nitrate obtain mixed liquor；
It is evaporated described mixed liquor processing, obtains Ag doping graphene oxide composite paper；And
Described Ag doping graphene oxide composite paper is put into the solution containing reducing agent carries out reduction treatment,
Obtain Ag doping Graphene extrusion coating paper.
Wherein in an embodiment, the described method preparing graphene oxide particularly as follows:
Under the conditions of ice-water bath, by native graphite and sodium nitrate mix homogeneously, add concentrated sulphuric acid, stirring
10min～150min, is subsequently adding potassium permanganate, continues stirring 10min～150min, obtains mixed liquor；
Described mixed liquor is moved in 20 DEG C～40 DEG C of waters bath with thermostatic control, stirring reaction 15min～180min；To institute
State addition deionized water in mixed liquor, react 30min～60min, then by described 20 DEG C～40 DEG C of waters bath with thermostatic control
Temperature rise to 80 DEG C～100 DEG C, stir 30min～300min；It is eventually adding hydrogen peroxide, reaction
30min～90min, washs, is dried to obtain graphene oxide.
Wherein in an embodiment, described silver nitrate with the mass ratio of described graphene oxide is
0.01～1:1～5.
Wherein in an embodiment, described described mixed liquor is evaporated process operation particularly as follows: in
Evaporate 0.5 hour～24 hours at 30 DEG C～150 DEG C.
Wherein in an embodiment, described described mixed liquor is evaporated process operation particularly as follows: in
Evaporate 6 hours～12 hours at 60 DEG C～100 DEG C.
Wherein in an embodiment, described reducing agent is in sodium borohydride, ascorbic acid and hydrazine hydrate
At least one.
Wherein in an embodiment, in the described solution containing reducing agent, solvent selected from methanol, ethanol,
At least one in oxolane and dimethylformamide.
Wherein in an embodiment, the concentration of the described solution containing reducing agent is 0.01mol/L～5mol/L.
Wherein in an embodiment, described described Ag doping graphene oxide composite paper is put into containing reduction
The solution of agent carries out the step of reduction treatment particularly as follows: the described solution containing reducing agent is heated to 30 DEG C
～150 DEG C, described Ag doping graphene oxide composite paper is put into temperature be 30 DEG C～150 DEG C containing reducing agent
Solution in react 0.5 hour～10 hours.
Ag doping Graphene extrusion coating paper prepared by the preparation method of a kind of above-mentioned Ag doping Graphene extrusion coating paper.
The preparation method of above-mentioned Ag doping Graphene extrusion coating paper first prepares graphene oxide, then prepares graphite oxide
Alkene suspension, evaporation process graphene oxide suspension and the mixed liquor of silver nitrate, obtain Ag doping oxidation stone
Ink alkene extrusion coating paper, carries out reduction treatment by this Ag doping graphene oxide composite paper and i.e. obtains Ag doping Graphene
Extrusion coating paper.The method is relative to vacuum filtration method, and reaction condition is gentle, and low for equipment requirements, technique is simple.
Further, our experiments show that, the thermal conductivity of the vertical direction of preparation-obtained Ag doping Graphene extrusion coating paper is relatively
High.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the Ag doping Graphene extrusion coating paper of an embodiment；
Fig. 2 is the SEM figure of the Ag doping Graphene extrusion coating paper of embodiment 1.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, the most right
The detailed description of the invention of the present invention is described in detail.Elaborate in the following description a lot of detail with
It is easy to fully understand the present invention.But the present invention can come real to be a lot different from alternate manner described here
Executing, those skilled in the art can do similar improvement in the case of intension of the present invention, therefore this
Bright do not limited by following public being embodied as.
Refer to Fig. 1, the preparation method of the Ag doping Graphene extrusion coating paper of an embodiment, comprise the steps
S110～step S140.
Step S110: prepare graphene oxide, carries out supersound process by graphene oxide, prepares oxidation
Graphene suspension.
Prepare the method for graphene oxide particularly as follows:
Step S210: under the conditions of ice-water bath, by uniform to native graphite and sodium nitrate mixture, adds dense sulfur
Acid, stirs 10min～150min, is subsequently adding potassium permanganate, continues stirring 15min～150min, is mixed
Close liquid.
Step S220: mixed liquor is moved in 20 DEG C～40 DEG C of waters bath with thermostatic control, stirring reaction 15min～180min；
In mixed liquor, add deionized water, react 30min～60min, then by the temperature of 20 DEG C～40 DEG C waters bath with thermostatic control
Degree rises to 80 DEG C～100 DEG C, stirring reaction 30min～300min；It is eventually adding hydrogen peroxide, reaction
30min～90min, washs, is dried to obtain graphene oxide.
Preferably, the mass volume ratio of native graphite, sodium nitrate and concentrated sulphuric acid is 1～5g:1～5g:46～230mL.
Native graphite is 1～5:6～30 with the mass ratio of potassium permanganate, preferably 1～5:6～24.
Preferably, the volume ratio of concentrated sulphuric acid, deionized water and hydrogen peroxide is 46～230:92～460:40～200.
It is further preferred that the mass concentration of concentrated sulphuric acid is 95%～98%, the mass concentration of hydrogen peroxide is 30%.
In step S210, the stir speed (S.S.) of two stirring operations is 300r/min～1000r/min, is preferably
300r/min～600r/min.
In step S220, the stir speed (S.S.) of two stirring operations is 300r/min～800r/min, is preferably
300r/min～600r/min.
The method of washing is particularly as follows: use hydrogen peroxide, hydrochloric acid and distilled water eccentric cleaning successively.Preferably, double
The mass concentration of oxygen water is 30%, and the mass concentration of hydrochloric acid is 10%.Centrifugal rotating speed is
500r/min～10000r/min, the centrifugal time is 10min～60min.
The method being dried can be with lyophilization, forced air drying or vacuum drying.
The graphene oxide prepared is added to the water, carries out supersound process, obtain graphene oxide and suspend
Liquid.Preferably, the power of supersound process is 1000W, and the time is 1h～4h.
Preferably, the concentration of graphene oxide suspension is 0.5g/L～5g/L.
Step S120: add silver nitrate in graphene oxide suspension and obtain mixed liquor.
Silver nitrate is 0.01～1:1～5 with the mass ratio of graphene oxide, preferably 0.1～0.5:2～3.To oxidation
Graphene suspension adds silver nitrate, stirs 0.5 hour～2 hours under 300r/min, mix homogeneously,
Obtain mixed liquor.
Step S130: be evaporated mixed liquor processing, obtain Ag doping graphene oxide composite paper.
It is evaporated mixed liquor processing, with solvent evaporated, and makes Ag doping in graphene oxide.Evaporation
The operation processed, particularly as follows: put in air dry oven by mixed liquor, evaporates 0.5 little at 30 DEG C～150 DEG C
Time～24 hours.
Preferably, the temperature of evaporation process is 60 DEG C～100 DEG C, and the time is 6 hours～12 hours.
Step S140: Ag doping graphene oxide composite paper is put in the solution containing reducing agent and reduces
Process, obtain Ag doping Graphene extrusion coating paper.
Preferably, at least one in sodium borohydride, ascorbic acid and hydrazine hydrate of reducing agent.
In solution containing reducing agent, in solvent selected from methanol, ethanol, oxolane and dimethylformamide
At least one.
It is further preferred that the concentration of the solution containing reducing agent is 0.01mol/L～5mol/L, more preferably
0.05mol/L～1mol/L.
Ag doping graphene oxide composite paper is put into the step carrying out reduction treatment in the solution containing reducing agent
Particularly as follows: the solution containing reducing agent is heated to 30 DEG C～150 DEG C, by Ag doping graphene oxide composite paper
Put in the solution containing reducing agent that temperature is 30 DEG C～150 DEG C and react 0.5 hour～10 hours, be preferably
0.5 hour～5 hours.
Preferably, in reduction process, the temperature of the solution containing reducing agent is 40 DEG C～100 DEG C.
The preparation method of above-mentioned Ag doping Graphene extrusion coating paper first prepares graphene oxide, then prepares graphite oxide
Alkene suspension, evaporation process graphene oxide suspension and the mixed liquor of silver nitrate, obtain Ag doping oxidation stone
Ink alkene extrusion coating paper, carries out reduction treatment by this Ag doping graphene oxide composite paper and i.e. obtains Ag doping Graphene
Extrusion coating paper.The method is gentle relative to vacuum filtration method reaction condition, low for equipment requirements, and technique is simple,
Easily realize industrialization.Further, our experiments show that, preparation-obtained Ag doping Graphene extrusion coating paper vertical
The thermal conductivity in direction is higher.
The preparation method of above-mentioned Ag doping Graphene extrusion coating paper can prepare the Ag doping that thickness is 0.5 μm～2mm
Graphene extrusion coating paper, its in-plane thermal conductivity is 200～700W/mK, and vertical direction thermal conductivity is 2～5
W/mK, sheet resistance is 1～200 Ω/.The Ag doping Graphene extrusion coating paper of this performance can be widely applied for electronics
Encapsulation field.
It is expanded on further below by way of specific embodiment.
Assay method in following example is as follows:
(1) thermal conductivity: use the boundary material thermal resistance of ASTM D 5470-06 Specification Design manufacture and heat to pass
Leading coefficient measuring equipment to be measured, its model is LW-9389；
(2) sheet resistance test: using the four detecting probe surface resistance meters that u s company produces, its model is
PRO4-6000。
Embodiment 1
Under the conditions of ice-water bath, 1g native graphite is mixed homogeneously with 1g sodium nitrate, add the dense of 46ml
Sulphuric acid, stirs 10min under the conditions of 1000r/min；Add 6g potassium permanganate, under the conditions of 600r/min
Stirring 30min obtains mixed liquor；Above-mentioned mixed liquor is moved in 35 DEG C of water-baths, stirring reaction 60min；Again
Add the deionized water of 92mL, react 30min, by the warming-in-water of 35 DEG C to 98 DEG C, stirring reaction 60min；
It is eventually adding the hydrogen peroxide that 40mL mass concentration is 30%, continues reaction 30min until solution becomes bright orange
Color.It is 10% by the hydrogen peroxide that mass concentration is 30%, mass concentration successively by reacting mixed solution completely
Hydrochloric acid and distilled water be centrifuged clean and be dried, it is thus achieved that graphene oxide, the speed of eccentric cleaning is
500r/min, the time is 60min.Weigh graphene oxide powder 0.5g, add 1L deionized water, ultrasonic
Processing 60min, power is 1000W, it is thus achieved that mass concentration is the graphene oxide suspension of 0.5g/L.To
Graphene oxide suspension adds 0.1g silver nitrate, under the conditions of 300r/min, stirs 60min, mixed
Close liquid.Mixed liquor is placed in the air dry oven of 80 DEG C again and is evaporated processing 12 hours, it is thus achieved that Ag doping
Graphene oxide composite paper.Finally Ag doping graphene oxide composite paper being immersed molar concentration is 0.5mol/L
Sodium borohydride ethanol solution in carry out electronation, reaction temperature is 150 DEG C, and the response time is 0.5 little
Time, it is thus achieved that Ag doping Graphene extrusion coating paper.The Ag doping stone of 55 μ m-thick can be prepared by said method
Ink alkene extrusion coating paper, horizontal direction thermal conductivity is 200W/mK, and vertical thermal conductance is 2.7W/mK, and sheet resistance is
109Ω/□。
Fig. 2 is the SEM figure of the Ag doping Graphene extrusion coating paper of the present embodiment 1 preparation, as seen from Figure 2,
The present embodiment 1 prepares multiple Ag doping Graphene extrusion coating paper.
Embodiment 2
Under the conditions of ice-water bath, 1g native graphite is mixed homogeneously with 1g sodium nitrate, add the dense of 46ml
Sulphuric acid, stirs 150min under the conditions of 300r/min；Add 6g potassium permanganate, under the conditions of 300r/min
Stirring 60min obtains mixed liquor；Above-mentioned mixed liquor is moved in 20 DEG C of water-baths, stirring reaction 180min；Again
Add the deionized water of 92mL, react 30min, by the warming-in-water of 20 DEG C to 98 DEG C, stirring reaction
120min；It is eventually adding the hydrogen peroxide that 40mL mass concentration is 30%, continues reaction 30min until solution
Become glassy yellow.Carry out reacting mixed solution completely successively by the hydrogen peroxide that mass concentration is 30%, matter
Amount concentration be 10% hydrochloric acid and distilled water be centrifuged cleaning and being dried, it is thus achieved that graphene oxide, centrifugal clear
The speed washed is 10000r/min, and the time is 10min.Weigh graphene oxide powder 2.5g, add 0.5L
Deionized water, supersound process 4h, power is 1000W, it is thus achieved that mass concentration is that the graphene oxide of 5g/L hangs
Supernatant liquid.In graphene oxide suspension, add 0.5g silver nitrate, under the conditions of 300r/min, stir 2h,
To mixed liquor.Mixed liquor is placed in the air dry oven of 90 DEG C again and is evaporated processing 10 hours, it is thus achieved that silver
Doping graphene oxide composite paper.By Ag doping graphene oxide composite paper immersion molar concentration it is finally
Carrying out electronation in the ethanol solution of the ascorbic acid of 1mol/L, reaction temperature is 60 DEG C, and the response time is
2 hours, it is thus achieved that Ag doping Graphene extrusion coating paper.The Ag doping of 25 μ m-thick can be prepared by said method
Graphene paper, horizontal direction thermal conductivity is 700W/mK, and vertical thermal conductance is 3.5W/mK, and sheet resistance is
25Ω/□。
Embodiment 3
Under the conditions of ice-water bath, 2g native graphite is mixed homogeneously with 4g sodium nitrate, adds 182ml's
Concentrated sulphuric acid, stirs 15min under the conditions of 800r/min；Add 18g potassium permanganate, in 800r/min condition
Lower stirring 15min obtains mixed liquor；Above-mentioned mixed liquor is moved in 40 DEG C of water-baths, stirring reaction 15min；
Add the deionized water of 182mL, react 60min, by the warming-in-water of 40 DEG C to 80 DEG C, stirring reaction
300min；Adding 80mL mass concentration is the hydrogen peroxide of 30%, continues reaction 90min until solution becomes
Glassy yellow.By reacting mixed solution completely by the hydrogen peroxide that mass concentration is 30%, mass concentration it is successively
The hydrochloric acid of 10% and distilled water are centrifuged cleaning and being dried, it is thus achieved that graphene oxide, the speed of eccentric cleaning is
5000r/min, the time is 30min.Weigh graphene oxide powder 2g, add 0.5L deionized water, ultrasonic
Processing 4h, power is 1000W, it is thus achieved that mass concentration is the graphene oxide suspension of 4g/L.To oxidation stone
Ink alkene suspension adds 0.5g silver nitrate, under the conditions of 300r/min, stirs 2h, obtain mixed liquor.Again will
Mixed liquor is placed in the air dry oven of 100 DEG C and is evaporated processing 6 hours, it is thus achieved that Ag doping graphene oxide
Extrusion coating paper.Finally Ag doping graphene oxide composite paper being immersed molar concentration is the ascorbic acid of 0.05mol/L
Ethanol solution in carry out electronation, reaction temperature is 30 DEG C, and the response time is 2 hours, it is thus achieved that silver is mixed
Miscellaneous Graphene extrusion coating paper.The Ag doping graphene paper of 40 μ m-thick, level can be prepared by said method
Direction thermal conductivity be 570W/mK vertical thermal conductance be 3.2W/mK, sheet resistance is 70 Ω/.
Embodiment 4
Under the conditions of ice-water bath, 3g native graphite is mixed homogeneously with 5g sodium nitrate, adds 230ml's
Concentrated sulphuric acid, stirs 15min under the conditions of 300r/min；Add 30g potassium permanganate, in 500r/min condition
Lower stirring 100min obtains mixed liquor；Above-mentioned mixed liquor is moved in 35 DEG C of water-baths, react 150min；Again
Add the deionized water of 460mL, react 45min, by the warming-in-water of 35 DEG C to 100 DEG C, stirring reaction
30min；Adding 200mL mass concentration is the hydrogen peroxide of 30%, continues reaction 60min until solution becomes
Glassy yellow.By reacting mixed solution completely by the hydrogen peroxide that mass concentration is 30%, mass concentration it is successively
The hydrochloric acid of 10% and distilled water are centrifuged cleaning and being dried, it is thus achieved that graphene oxide, the speed of eccentric cleaning is
1000r/min, the time is 45min.Weigh graphene oxide powder 1g, add 0.5L deionized water, ultrasonic
Processing 2h, power is 1000W, it is thus achieved that mass concentration is the graphene oxide suspension of 1g/L.To oxidation stone
Ink alkene suspension adds 0.01g silver nitrate, under the conditions of 300r/min, stirs 30min, obtain mixed liquor.
Mixed liquor is placed in the air dry oven of 30 DEG C again and is evaporated processing 12 hours, it is thus achieved that Ag doping oxidation stone
Ink alkene extrusion coating paper.Finally Ag doping graphene oxide composite paper being immersed molar concentration is the hydroboration of 5mol/L
Carrying out electronation in the methanol solution of sodium, reaction temperature is 100 DEG C, and the response time is 5 hours, it is thus achieved that silver
Doped graphene extrusion coating paper.The Ag doping graphene paper of 30 μ m-thick, water can be prepared by said method
Square to thermal conductivity be 602W/mK vertical thermal conductance be 3.3W/mK, sheet resistance is 65 Ω/.
Embodiment 5
Under the conditions of ice-water bath, 2.5g native graphite is mixed homogeneously with 5g sodium nitrate, adds 200ml
Concentrated sulphuric acid, under the conditions of 300r/min stir 15min；Add 15g potassium permanganate, at 500r/min bar
Stir 100min under part and obtain mixed liquor；Above-mentioned mixed liquor is moved in 35 DEG C of water-baths, react 150min；
Adding the deionized water of 460mL, react 45min, by the warming-in-water of 35 DEG C to 100 DEG C, stirring is anti-
Answer 30min；Adding 200mL mass concentration is the hydrogen peroxide of 30%, continues reaction 60min until solution becomes
For glassy yellow.By react completely mixed solution successively by the hydrogen peroxide that mass concentration is 30%, mass concentration
Be 10% hydrochloric acid and distilled water be centrifuged clean and be dried, it is thus achieved that graphene oxide, the speed of eccentric cleaning
Rate is 2000r/min, and the time is 30min.Weigh graphene oxide powder 1g, add 0.5L deionized water,
Supersound process 2h, power is 1000W, it is thus achieved that mass concentration is the graphene oxide suspension of 1g/L.To oxygen
Functionalized graphene suspension adds 0.01g silver nitrate, under the conditions of 300r/min, stirs 30min, mixed
Liquid.Mixed liquor is placed in the air dry oven of 30 DEG C again and is evaporated processing 12 hours, it is thus achieved that Ag doping oxygen
Functionalized graphene extrusion coating paper.Finally Ag doping graphene oxide composite paper being immersed molar concentration is containing of 5mol/L
Have in the solution of reducing agent and carry out electronation, in the solution containing reducing agent, reducing agent be mass ratio be 1:1
Ascorbic acid and hydrazine hydrate, solvent be volume ratio be oxolane and the dimethylformamide of 1:1.Reaction temperature
Degree is 40 DEG C, and the response time is 5 hours, it is thus achieved that Ag doping Graphene extrusion coating paper.Can be made by said method
The standby Ag doping graphene paper obtaining 30 μ m-thick, horizontal direction thermal conductivity is 479W/mK, vertical thermal conductance
For 3.1W/mK, sheet resistance is 73 Ω/.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is as the criterion.
Claims (7)
1. a preparation method for Ag doping Graphene extrusion coating paper, comprises the steps:
Prepare graphene oxide, described graphene oxide is carried out supersound process, prepares graphene oxide
Suspension；
In described graphene oxide suspension, add silver nitrate obtain mixed liquor；
It is evaporated described mixed liquor processing, obtains Ag doping graphene oxide composite paper；And
Described Ag doping graphene oxide composite paper is put into the solution containing reducing agent carries out reduction treatment,
Obtain Ag doping Graphene extrusion coating paper；
The described operation being evaporated described mixed liquor processing is particularly as follows: evaporate 0.5 at 30 DEG C～150 DEG C
Hour～24 hours；
Described being put into by described Ag doping graphene oxide composite paper carries out also original place in the solution containing reducing agent
The step of reason is particularly as follows: be heated to 30 DEG C～150 DEG C by the described solution containing reducing agent, by described Ag doping
Graphene oxide composite paper is put in the solution containing reducing agent that temperature is 30 DEG C～150 DEG C and is reacted 0.5 hour
～10 hours.
The preparation method of Ag doping Graphene extrusion coating paper the most according to claim 1, it is characterised in that
The described method preparing graphene oxide particularly as follows:
Under the conditions of ice-water bath, by native graphite and sodium nitrate mix homogeneously, add concentrated sulphuric acid, stirring
10min～150min, is subsequently adding potassium permanganate, continues stirring 10min～150min, obtains mixed liquor；
Described mixed liquor is moved in 20 DEG C～40 DEG C of waters bath with thermostatic control, stirring reaction 15min～180min；To institute
State addition deionized water in mixed liquor, react 30min～60min, then by described 20 DEG C～40 DEG C of waters bath with thermostatic control
Temperature rise to 80 DEG C～100 DEG C, stir 30min～300min；It is eventually adding hydrogen peroxide, reaction
30min～90min, washs, is dried to obtain graphene oxide.
The preparation method of Ag doping Graphene extrusion coating paper the most according to claim 1, it is characterised in that
Described silver nitrate is 0.01～1:1～5 with the mass ratio of described graphene oxide.
The preparation method of Ag doping Graphene extrusion coating paper the most according to claim 1, it is characterised in that
The described operation being evaporated described mixed liquor processing is particularly as follows: evaporate 6 hours～12 at 60 DEG C～100 DEG C
Hour.
The preparation method of Ag doping Graphene extrusion coating paper the most according to claim 1, it is characterised in that
At least one in sodium borohydride, ascorbic acid and hydrazine hydrate of described reducing agent.
The preparation method of Ag doping Graphene extrusion coating paper the most according to claim 1, it is characterised in that
In the described solution containing reducing agent, in solvent selected from methanol, ethanol, oxolane and dimethylformamide
At least one.
The preparation method of Ag doping Graphene extrusion coating paper the most according to claim 1, it is characterised in that
The concentration of the described solution containing reducing agent is 0.01mol/L～5mol/L.
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| CN201410361337.5A CN104163420B (en) | 2014-07-25 | 2014-07-25 | Ag doping Graphene extrusion coating paper and preparation method thereof |
| PCT/CN2015/084015 WO2016011905A1 (en) | 2014-07-25 | 2015-07-14 | Silver-doped graphene composite paper and preparation method therefor |
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| CN104163420B (en) * | 2014-07-25 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Ag doping Graphene extrusion coating paper and preparation method thereof |
| CN104891477B (en) * | 2015-05-15 | 2016-11-09 | 北京交通大学 | A kind of simple and environmentally-friendly graphene paper preparation method |
| CN105399084A (en) * | 2015-12-01 | 2016-03-16 | 天津工业大学 | Preparation method of powder type graphene oxide |
| CN106698402A (en) * | 2017-01-05 | 2017-05-24 | 东南大学 | Production method of metal nano-particle doped flexible self-supporting graphene film |
| CN106865537B (en) * | 2017-03-17 | 2019-05-28 | 吉林大学 | A kind of preparation method of high strength graphite alkenyl extrusion coating paper |
| CN111972435A (en) * | 2019-05-24 | 2020-11-24 | 浙江海纳新材料科技有限公司 | Preparation method of nano-silver-graphene oxide composite material |
| CN111392717B (en) * | 2020-03-25 | 2021-08-06 | 浙江墨原新材料有限公司 | Preparation method of concentrated graphene oxide solution and heat conducting film |
| CN112118708B (en) * | 2020-09-10 | 2023-03-21 | 安徽工业大学 | Heat-conducting film and preparation method thereof |
| CN113774725B (en) * | 2021-08-25 | 2023-01-10 | 浙江金华丁丁实业有限公司 | Preparation method of white paperboard containing graphene heat conduction layer and having good ink absorption |
| CN114260460A (en) * | 2021-12-24 | 2022-04-01 | 陕西煤业化工技术研究院有限责任公司 | Submicron graphene silver powder suitable for 5G field and preparation method and application thereof |
| CN116814146A (en) * | 2023-07-05 | 2023-09-29 | 扬州市德运塑业科技股份有限公司 | Graphene-based antibacterial and wear-resistant automotive interior leather and preparation method thereof |
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| CN101948108B (en) * | 2010-10-02 | 2012-05-09 | 上海交通大学 | Preparation method of oxidized graphite paper |
| CN102827315B (en) * | 2012-08-30 | 2015-03-25 | 合肥工业大学 | Graphene oxide/polystyrene nano composite and preparation method thereof |
| CN102903531B (en) * | 2012-11-06 | 2015-08-12 | 东华大学 | A kind of preparation method of composite electrode material for super capacitor |
| CN103285845B (en) * | 2013-05-20 | 2015-05-13 | 陕西科技大学 | Preparation method of graphene oxide wrapped titania microsphere photocatalyst |
| CN103334096B (en) * | 2013-07-02 | 2015-12-23 | 江苏大学 | A kind of method preparing nano-silver-graphenecomposite composite film |
| CN103545053B (en) * | 2013-10-25 | 2016-03-09 | 深圳市华星光电技术有限公司 | The preparation method of transparent conductive film and there is the preparation method of CF substrate of this conductive film |
| CN103639421B (en) * | 2013-12-04 | 2016-06-08 | 北京印刷学院 | A kind of preparation method of the Graphene/argentum nano composite material of high conductivity |
| CN104163420B (en) * | 2014-07-25 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Ag doping Graphene extrusion coating paper and preparation method thereof |
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