CN104163420A - Silver-doped graphene composite paper and preparation method - Google Patents
Silver-doped graphene composite paper and preparation method Download PDFInfo
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- CN104163420A CN104163420A CN201410361337.5A CN201410361337A CN104163420A CN 104163420 A CN104163420 A CN 104163420A CN 201410361337 A CN201410361337 A CN 201410361337A CN 104163420 A CN104163420 A CN 104163420A
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Abstract
The invention relates to silver-doped graphene composite paper and its preparation method. The preparation method of the silver-doped graphene composite paper comprises the following steps: preparing graphene oxide, and carrying out an ultrasonic treatment on graphene oxide to prepare a graphene oxide suspension; adding silver nitrate into the graphene oxide suspension to obtain a mixed liquor; evaporating the mixed liquor to obtain silver-doped graphene oxide composite paper; and carrying out a reduction treatment by putting the silver-doped graphene oxide composite paper into a solution containing a reducing agent so as to obtain the silver-doped graphene composite paper. In comparison with a vacuum filtration method, the method provided by the invention has advantages of mild reaction condition, low requirements on equipment and simple process. In addition, it shows through experiments that the thermal conductivity of the prepared silver-doped graphene composite paper is high in the vertical direction.
Description
Technical field
The present invention relates to electronic package material field, particularly relate to silver-colored doped graphene Composite Paper and preparation method thereof.
Background technology
Along with electron device is to the development of integrated, the high computing of height field, heat radiation becomes a difficult problem.All the time, the traditional heat-dissipating such as copper, silver material is widely used in electron device and product heat radiation.But copper, ag material are expensive, and easily oxidized, density is high, and thermal expansivity is large, and carbon material rises gradually due to a series of excellent specific properties such as high heat conduction, low density, low thermal coefficient of expansion and reserves are abundant, cheap.Research shows that the thermal conductivity of common carbon nanotube is 3000～3500W/mK, and diamond is 1000～2200W/mK, and the thermal conductivity of single-layer graphene is especially up to 5300W/mK.
Graphene is the novel material of individual layer atomic building, and its carbon atom is with sp
2hybridized orbital forms hexagonal honeycomb lattice.All the time, Graphene is considered to hypothetical structure, separately stable existence.2004, the physicist Andre Geim of Univ Manchester UK and Konstantin Novoselov utilized adhesive tape from graphite, repeatedly to glue lower thin slice, finally successfully isolate Graphene.Graphene, due to its special physical structure, has a series of excellent specific properties: the nano material that world is thin, the hardest is almost completely transparent, only absorbs 2.3% light; Thermal conductivity is up to 5300 W/mK, higher than carbon nanotube and diamond; Under normal temperature, its electronic mobility surpasses 15000cm
2/ Vs, again ratio nano carbon pipe or silicon wafer height; And resistivity only approximately 10
-6Ω cm, lower than copper or silver, be the material of world resistivity minimum.The Kong Qingqiang of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences etc. utilizes vacuum filtration that chopped carbon fiber and graphene oxide are prepared into Composite Paper, by high-temperature thermal annealing, obtain Graphene Composite Paper again, thermal conductivity in its horizontal plane is up to 977W/mK, but the thermal conductivity of vertical direction only has 0.38W/mK.And the product area that vacuum filtration obtains is little, high-temperature thermal annealing power consumption is large, is not suitable for suitability for industrialized production, need to find a kind of simple method, realizes scale operation, and the thermal conductivity of the product vertical direction obtaining will have lifting by a relatively large margin.
Summary of the invention
Based on this, be necessary to provide a kind of technique simple silver-colored doped graphene Composite Paper, to prepare the higher silver-colored doped graphene Composite Paper of thermal conductivity of vertical direction.
Further, provide a kind of silver-colored doped graphene Composite Paper being prepared by the preparation method of above-mentioned silver-colored doped graphene Composite Paper.
A preparation method for silver-colored doped graphene Composite Paper, comprises the steps:
Prepare graphene oxide, described graphene oxide is carried out to supersound process, prepare graphene oxide suspension;
In described graphene oxide suspension, add Silver Nitrate to obtain mixed solution;
Described mixed solution is carried out to evaporation process, obtain silver doping graphene oxide composite paper; And
Described silver doping graphene oxide composite paper is put into the solution that contains reductive agent and reduce processing, obtain silver-colored doped graphene Composite Paper.
In an embodiment, the described method of preparing graphene oxide is specially therein:
Under ice-water bath condition, natural graphite and SODIUMNITRATE are mixed, add the vitriol oil, stir 10min～150min, then add potassium permanganate, continue to stir 10min～150min, obtain mixed solution;
Described mixed solution is moved in 20 ℃～40 ℃ waters bath with thermostatic control to stirring reaction 15min～180min; In described mixed solution, add deionized water, reaction 30min～60min, then rises to 80 ℃～100 ℃ by the temperature of described 20 ℃～40 ℃ of waters bath with thermostatic control, stirs 30min～300min; Finally add hydrogen peroxide, reaction 30min～90min, washing, the dry graphene oxide that obtains.
In an embodiment, the mass ratio of described Silver Nitrate and described graphene oxide is 0.01～1:1～5 therein.
Therein in an embodiment, the described operation that described mixed solution is carried out to evaporation process is specially: at 30 ℃～150 ℃, evaporate 0.5 hour～24 hours.
Therein in an embodiment, the described operation that described mixed solution is carried out to evaporation process is specially: at 60 ℃～100 ℃, evaporate 6 hours～12 hours.
In an embodiment, described reductive agent is selected from least one in sodium borohydride, xitix and hydrazine hydrate therein.
Therein in an embodiment, described in contain reductive agent solution in, solvent is selected from least one in methyl alcohol, ethanol, tetrahydrofuran (THF) and dimethyl formamide.
Therein in an embodiment, described in contain reductive agent the concentration of solution be 0.01mol/L～5mol/L.
Therein in an embodiment, describedly described silver doping graphene oxide composite paper is put into the solution that contains reductive agent reduce the step of processing and be specially: the described solution that contains reductive agent is heated to 30 ℃～150 ℃, and described silver is adulterated, and to put into temperature be that the solution that contains reductive agent of 30 ℃～150 ℃ reacts 0.5 hour～10 hours to graphene oxide composite paper.
Silver-colored doped graphene Composite Paper prepared by a kind of preparation method of above-mentioned silver-colored doped graphene Composite Paper.
The preparation method of above-mentioned silver-colored doped graphene Composite Paper first prepares graphene oxide, prepare again graphene oxide suspension, the mixed solution of evaporation process graphene oxide suspension and Silver Nitrate, obtain silver doping graphene oxide composite paper, this silver doping graphene oxide composite paper reduce to processing and obtain silver-colored doped graphene Composite Paper.The method is with respect to vacuum filtration method, and reaction conditions is gentle, and low for equipment requirements, technique is simple.And, our experiments show that, the thermal conductivity of the vertical direction of preparation-obtained silver-colored doped graphene Composite Paper is higher.
Accompanying drawing explanation
Fig. 1 is preparation method's the schema of the silver-colored doped graphene Composite Paper of an embodiment;
Fig. 2 is the SEM figure of the silver-colored doped graphene Composite Paper of embodiment 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the silver-colored doped graphene Composite Paper of an embodiment, comprises the steps S110～step S140.
Step S110: prepare graphene oxide, graphene oxide is carried out to supersound process, prepare graphene oxide suspension.
The method of preparing graphene oxide is specially:
Step S210: under ice-water bath condition, natural graphite and sodium nitrate mixture is even, add the vitriol oil, stir 10min～150min, then add potassium permanganate, continue to stir 15min～150min, obtain mixed solution.
Step S220: mixed solution is moved in 20 ℃～40 ℃ waters bath with thermostatic control to stirring reaction 15min～180min; In mixed solution, add deionized water, reaction 30min～60min, then rises to 80 ℃～100 ℃ by the temperature of 20 ℃～40 ℃ of waters bath with thermostatic control, stirring reaction 30min～300min; Finally add hydrogen peroxide, reaction 30min～90min, washing, the dry graphene oxide that obtains.
Preferably, the mass volume ratio of natural graphite, SODIUMNITRATE and the vitriol oil is 1～5g:1～5g:46～230mL.The mass ratio of natural graphite and potassium permanganate is 1～5:6～30, is preferably 1～5:6～24.
Preferably, the volume ratio of the vitriol oil, deionized water and hydrogen peroxide is 46～230:92～460:40～200.
Further preferably, the mass concentration of the vitriol oil is 95%～98%, and 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 specially: use successively hydrogen peroxide, hydrochloric acid and distilled water eccentric cleaning.Preferably, the mass concentration of hydrogen peroxide is 30%, and the mass concentration of hydrochloric acid is 10%.Centrifugal rotating speed is 500r/min～10000r/min, and the centrifugal time is 10min～60min.
Dry method can lyophilize, forced air drying or vacuum-drying.
The graphene oxide preparing is added to the water, carries out supersound process, obtain graphene oxide suspension.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 to obtain mixed solution in graphene oxide suspension.
The mass ratio of Silver Nitrate and graphene oxide is 0.01～1:1～5, is preferably 0.1～0.5:2～3.In graphene oxide suspension, add Silver Nitrate, under 300r/min, stir 0.5 hour～2 hours, mix, obtain mixed solution.
Step S130: mixed solution is carried out to evaporation process, obtain silver doping graphene oxide composite paper.
Mixed solution is carried out to evaporation process, with solvent evaporated, and silver is doped in graphene oxide.The operation of evaporation process is specially: mixed solution is put into air dry oven, evaporate 0.5 hour～24 hours at 30 ℃～150 ℃.
Preferably, the temperature of evaporation process is 60 ℃～100 ℃, and the time is 6 hours～12 hours.
Step S140: the silver graphene oxide composite paper that adulterates is put into the solution that contains reductive agent and reduced processing, obtain silver-colored doped graphene Composite Paper.
Preferably, reductive agent is selected from least one in sodium borohydride, xitix and hydrazine hydrate.
In the solution that contains reductive agent, solvent is selected from least one in methyl alcohol, ethanol, tetrahydrofuran (THF) and dimethyl formamide.
Further preferably, the concentration of the solution that contains reductive agent is 0.01mol/L～5mol/L, more preferably 0.05mol/L～1mol/L.
The silver graphene oxide composite paper that adulterates is put into the solution that contains reductive agent and reduced the step of processing and be specially: the solution that contains reductive agent is heated to 30 ℃～150 ℃, silver is adulterated, and to put into temperature be that the solution that contains reductive agent of 30 ℃～150 ℃ reacts 0.5 hour～10 hours to graphene oxide composite paper, is preferably 0.5 hour～5 hours.
Preferably, in reduction process, the temperature of the solution that contains reductive agent is 40 ℃～100 ℃.
The preparation method of above-mentioned silver-colored doped graphene Composite Paper first prepares graphene oxide, prepare again graphene oxide suspension, the mixed solution of evaporation process graphene oxide suspension and Silver Nitrate, obtain silver doping graphene oxide composite paper, this silver doping graphene oxide composite paper reduce to processing and obtain silver-colored doped graphene Composite Paper.The method is gentle with respect to vacuum filtration method reaction conditions, and low for equipment requirements, technique is simple, easily realizes industrialization.And, our experiments show that, the thermal conductivity of the vertical direction of preparation-obtained silver-colored doped graphene Composite Paper is higher.
The preparation method of above-mentioned silver-colored doped graphene Composite Paper can prepare the silver-colored doped graphene Composite Paper that thickness is 0.5 μ m～2mm, and its in-plane thermal conductivity is 200～700W/mK, and vertical direction thermal conductivity is 2～5W/mK, and sheet resistance is 1～200 Ω/.The silver-colored doped graphene Composite Paper of this performance can be widely used in Electronic Packaging field.
By specific embodiment, further set forth below.
Measuring method in following examples is as follows:
(1) thermal conductivity: adopt boundary material thermal resistance and the heat-conduction coefficient measuring equipment of the manufacture of ASTM D 5470-06 Specification Design to measure, its model is LW-9389;
(2) sheet resistance test: the four point probe surface resistivity tester that adopts u s company to produce, its model is PRO4-6000.
Embodiment 1
Under ice-water bath condition, 1g natural graphite is mixed with 1g SODIUMNITRATE, then add the vitriol oil of 46ml, under 1000r/min condition, stir 10min; Add 6g potassium permanganate, under 600r/min condition, stir 30min and obtain mixed solution; Above-mentioned mixed solution is moved in 35 ℃ of water-baths to stirring reaction 60min; The deionized water that adds again 92mL, reaction 30min, by the warming-in-water to 98 ℃ of 35 ℃, stirring reaction 60min; Finally adding 40mL mass concentration is 30% hydrogen peroxide, continues reaction 30min until solution becomes glassy yellow.The hydrochloric acid that the hydrogen peroxide that is 30% by mass concentration successively by the mixing solutions reacting completely, mass concentration are 10% and distilled water carry out eccentric cleaning dry, obtain graphene oxide, and the speed of eccentric cleaning is 500r/min, and the time is 60min.Take graphene oxide powder 0.5g, add 1L deionized water, supersound process 60min, power is 1000W, the graphene oxide suspension that acquisition mass concentration is 0.5g/L.In graphene oxide suspension, add 0.1g Silver Nitrate, under 300r/min condition, stir 60min, obtain mixed solution.The air dry oven that mixed solution is placed in to 80 ℃ again carries out evaporation process 12 hours, obtains silver doping graphene oxide composite paper.In the ethanolic soln of the sodium borohydride that the graphene oxide composite paper that finally silver adulterated immersion volumetric molar concentration is 0.5mol/L, carry out chemical reduction, temperature of reaction is 150 ℃, and the reaction times is 0.5 hour, obtains silver-colored doped graphene Composite Paper.By aforesaid method, can prepare the silver-colored doped graphene Composite Paper that 55 μ m are thick, horizontal direction thermal conductivity is 200W/mK, and vertical heat conductance is 2.7W/mK, and sheet resistance is 109 Ω/.
Fig. 2 is the SEM figure of the silver-colored doped graphene Composite Paper of the present embodiment 1 preparation, and as seen from Figure 2, the present embodiment 1 prepares a plurality of silver-colored doped graphene Composite Papers.
Embodiment 2
Under ice-water bath condition, 1g natural graphite is mixed with 1g SODIUMNITRATE, then add the vitriol oil of 46ml, under 300r/min condition, stir 150min; Add 6g potassium permanganate, under 300r/min condition, stir 60min and obtain mixed solution; Above-mentioned mixed solution is moved in 20 ℃ of water-baths to stirring reaction 180min; The deionized water that adds again 92mL, reaction 30min, by the warming-in-water to 98 ℃ of 20 ℃, stirring reaction 120min; Finally adding 40mL mass concentration is 30% hydrogen peroxide, continues reaction 30min until solution becomes glassy yellow.The mixing solutions reacting completely is carried out to hydrochloric acid and distilled water that the hydrogen peroxide that is 30% by mass concentration successively, mass concentration are 10% and carry out eccentric cleaning dry, obtain graphene oxide, the speed of eccentric cleaning is 10000r/min, and the time is 10min.Take graphene oxide powder 2.5g, add 0.5L deionized water, supersound process 4h, power is 1000W, the graphene oxide suspension that acquisition mass concentration is 5g/L.In graphene oxide suspension, add 0.5g Silver Nitrate, under 300r/min condition, stir 2h, obtain mixed solution.The air dry oven that mixed solution is placed in to 90 ℃ again carries out evaporation process 10 hours, obtains silver doping graphene oxide composite paper.In the ethanolic soln of the xitix that the graphene oxide composite paper that finally silver adulterated immersion volumetric molar concentration is 1mol/L, carry out chemical reduction, temperature of reaction is 60 ℃, and the reaction times is 2 hours, obtains silver-colored doped graphene Composite Paper.By aforesaid method, can prepare the silver-colored doped graphene paper that 25 μ m are thick, horizontal direction thermal conductivity is 700W/mK, and vertical heat conductance is 3.5W/mK, and sheet resistance is 25 Ω/.
Embodiment 3
Under ice-water bath condition, 2g natural graphite is mixed with 4g SODIUMNITRATE, then add the vitriol oil of 182ml, under 800r/min condition, stir 15min; Add 18g potassium permanganate, under 800r/min condition, stir 15min and obtain mixed solution; Above-mentioned mixed solution is moved in 40 ℃ of water-baths to stirring reaction 15min; The deionized water that adds again 182mL, reaction 60min, by the warming-in-water to 80 ℃ of 40 ℃, stirring reaction 300min; Adding 80mL mass concentration is 30% hydrogen peroxide, continues reaction 90min until solution becomes glassy yellow.The hydrochloric acid that the hydrogen peroxide that is 30% by mass concentration successively by the mixing solutions reacting completely, mass concentration are 10% and distilled water carry out eccentric cleaning dry, obtain graphene oxide, and the speed of eccentric cleaning is 5000r/min, and the time is 30min.Take graphene oxide powder 2g, add 0.5L deionized water, supersound process 4h, power is 1000W, the graphene oxide suspension that acquisition mass concentration is 4g/L.In graphene oxide suspension, add 0.5g Silver Nitrate, under 300r/min condition, stir 2h, obtain mixed solution.The air dry oven that mixed solution is placed in to 100 ℃ again carries out evaporation process 6 hours, obtains silver doping graphene oxide composite paper.In the ethanolic soln of the xitix that the graphene oxide composite paper that finally silver adulterated immersion volumetric molar concentration is 0.05mol/L, carry out chemical reduction, temperature of reaction is 30 ℃, and the reaction times is 2 hours, obtains silver-colored doped graphene Composite Paper.By aforesaid method, can prepare the silver-colored doped graphene paper that 40 μ m are thick, horizontal direction thermal conductivity is that 570W/mK vertical heat conductance is 3.2W/mK, and sheet resistance is 70 Ω/.
Embodiment 4
Under ice-water bath condition, 3g natural graphite is mixed with 5g SODIUMNITRATE, then add the vitriol oil of 230ml, under 300r/min condition, stir 15min; Add 30g potassium permanganate, under 500r/min condition, stir 100min and obtain mixed solution; Above-mentioned mixed solution is moved in 35 ℃ of water-baths to reaction 150min; The deionized water that adds again 460mL, reaction 45min, by the warming-in-water to 100 ℃ of 35 ℃, stirring reaction 30min; Adding 200mL mass concentration is 30% hydrogen peroxide, continues reaction 60min until solution becomes glassy yellow.The hydrochloric acid that the hydrogen peroxide that is 30% by mass concentration successively by the mixing solutions reacting completely, mass concentration are 10% and distilled water carry out eccentric cleaning dry, obtain graphene oxide, and the speed of eccentric cleaning is 1000r/min, and the time is 45min.Take graphene oxide powder 1g, add 0.5L deionized water, supersound process 2h, power is 1000W, the graphene oxide suspension that acquisition mass concentration is 1g/L.In graphene oxide suspension, add 0.01g Silver Nitrate, under 300r/min condition, stir 30min, obtain mixed solution.The air dry oven that mixed solution is placed in to 30 ℃ again carries out evaporation process 12 hours, obtains silver doping graphene oxide composite paper.In the methanol solution of the sodium borohydride that the graphene oxide composite paper that finally silver adulterated immersion volumetric molar concentration is 5mol/L, carry out chemical reduction, temperature of reaction is 100 ℃, and the reaction times is 5 hours, obtains silver-colored doped graphene Composite Paper.By aforesaid method, can prepare the silver-colored doped graphene paper that 30 μ m are thick, horizontal direction thermal conductivity is that 602W/mK vertical heat conductance is 3.3W/mK, and sheet resistance is 65 Ω/.
Embodiment 5
Under ice-water bath condition, 2.5g natural graphite is mixed with 5g SODIUMNITRATE, then add the vitriol oil of 200ml, under 300r/min condition, stir 15min; Add 15g potassium permanganate, under 500r/min condition, stir 100min and obtain mixed solution; Above-mentioned mixed solution is moved in 35 ℃ of water-baths to reaction 150min; The deionized water that adds again 460mL, reaction 45min, by the warming-in-water to 100 ℃ of 35 ℃, stirring reaction 30min; Adding 200mL mass concentration is 30% hydrogen peroxide, continues reaction 60min until solution becomes glassy yellow.The hydrochloric acid that the hydrogen peroxide that is 30% by mass concentration successively by the mixing solutions reacting completely, mass concentration are 10% and distilled water carry out eccentric cleaning dry, obtain graphene oxide, and the speed of eccentric cleaning is 2000r/min, and the time is 30min.Take graphene oxide powder 1g, add 0.5L deionized water, supersound process 2h, power is 1000W, the graphene oxide suspension that acquisition mass concentration is 1g/L.In graphene oxide suspension, add 0.01g Silver Nitrate, under 300r/min condition, stir 30min, obtain mixed solution.The air dry oven that mixed solution is placed in to 30 ℃ again carries out evaporation process 12 hours, obtains silver doping graphene oxide composite paper.The graphene oxide composite paper that finally silver adulterated immerses in the solution that contains reductive agent that volumetric molar concentration is 5mol/L and carries out chemical reduction, in the solution that contains reductive agent, reductive agent is that mass ratio is xitix and the hydrazine hydrate of 1:1, and solvent is that volume ratio is tetrahydrofuran (THF) and the dimethyl formamide of 1:1.Temperature of reaction is 40 ℃, and the reaction times is 5 hours, obtains silver-colored doped graphene Composite Paper.By aforesaid method, can prepare the silver-colored doped graphene paper that 30 μ m are thick, horizontal direction thermal conductivity is 479W/mK, and vertical heat conductance is 3.1W/mK, and sheet resistance is 73 Ω/.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for silver-colored doped graphene Composite Paper, comprises the steps:
Prepare graphene oxide, described graphene oxide is carried out to supersound process, prepare graphene oxide suspension;
In described graphene oxide suspension, add Silver Nitrate to obtain mixed solution;
Described mixed solution is carried out to evaporation process, obtain silver doping graphene oxide composite paper; And
Described silver doping graphene oxide composite paper is put into the solution that contains reductive agent and reduce processing, obtain silver-colored doped graphene Composite Paper.
2. the preparation method of silver-colored doped graphene Composite Paper according to claim 1, is characterized in that, the described method of preparing graphene oxide is specially:
Under ice-water bath condition, natural graphite and SODIUMNITRATE are mixed, add the vitriol oil, stir 10min～150min, then add potassium permanganate, continue to stir 10min～150min, obtain mixed solution;
Described mixed solution is moved in 20 ℃～40 ℃ waters bath with thermostatic control to stirring reaction 15min～180min; In described mixed solution, add deionized water, reaction 30min～60min, then rises to 80 ℃～100 ℃ by the temperature of described 20 ℃～40 ℃ of waters bath with thermostatic control, stirs 30min～300min; Finally add hydrogen peroxide, reaction 30min～90min, washing, the dry graphene oxide that obtains.
3. the preparation method of silver-colored doped graphene Composite Paper according to claim 1, is characterized in that, the mass ratio of described Silver Nitrate and described graphene oxide is 0.01～1:1～5.
4. the preparation method of silver-colored doped graphene Composite Paper according to claim 1, is characterized in that, the described operation that described mixed solution is carried out to evaporation process is specially: at 30 ℃～150 ℃, evaporate 0.5 hour～24 hours.
5. the preparation method of silver-colored doped graphene Composite Paper according to claim 4, is characterized in that, the described operation that described mixed solution is carried out to evaporation process is specially: at 60 ℃～100 ℃, evaporate 6 hours～12 hours.
6. the preparation method of silver-colored doped graphene Composite Paper according to claim 1, is characterized in that, described reductive agent is selected from least one in sodium borohydride, xitix and hydrazine hydrate.
7. the preparation method of silver-colored doped graphene Composite Paper according to claim 1, is characterized in that, described in contain reductive agent solution in, solvent is selected from least one in methyl alcohol, ethanol, tetrahydrofuran (THF) and dimethyl formamide.
8. the preparation method of silver-colored doped graphene Composite Paper according to claim 1, is characterized in that, described in contain reductive agent the concentration of solution be 0.01mol/L～5mol/L.
9. the preparation method of silver-colored doped graphene Composite Paper according to claim 1, it is characterized in that, describedly described silver doping graphene oxide composite paper is put into the solution that contains reductive agent reduce the step of processing and be specially: the described solution that contains reductive agent is heated to 30 ℃～150 ℃, and described silver is adulterated, and to put into temperature be that the solution that contains reductive agent of 30 ℃～150 ℃ reacts 0.5 hour～10 hours to graphene oxide composite paper.
10. a silver-colored doped graphene Composite Paper of being prepared by the preparation method of the silver-colored doped graphene Composite Paper described in claim 1～9 any one.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948108A (en) * | 2010-10-02 | 2011-01-19 | 上海交通大学 | Optimized preparation method of oxidized graphite paper |
| CN102827315A (en) * | 2012-08-30 | 2012-12-19 | 合肥工业大学 | Graphene oxide/polystyrene nano composite and preparation method thereof |
| CN102903531A (en) * | 2012-11-06 | 2013-01-30 | 东华大学 | Method for preparing composite electrode material of super capacitor |
| CN103285845A (en) * | 2013-05-20 | 2013-09-11 | 陕西科技大学 | Preparation method of graphene oxide wrapped titania microsphere photocatalyst |
| CN103334096A (en) * | 2013-07-02 | 2013-10-02 | 江苏大学 | Method for preparing nano-silver-graphene composite film |
| CN103545053A (en) * | 2013-10-25 | 2014-01-29 | 深圳市华星光电技术有限公司 | Preparation method of transparent conducting thin film and preparation method of CF substrate with conducting thin film |
| CN103639421A (en) * | 2013-12-04 | 2014-03-19 | 北京印刷学院 | Preparation method for high-conductivity graphene and silver nanoparticle composite materials |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
-
2014
- 2014-07-25 CN CN201410361337.5A patent/CN104163420B/en active Active
-
2015
- 2015-07-14 WO PCT/CN2015/084015 patent/WO2016011905A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948108A (en) * | 2010-10-02 | 2011-01-19 | 上海交通大学 | Optimized preparation method of oxidized graphite paper |
| CN102827315A (en) * | 2012-08-30 | 2012-12-19 | 合肥工业大学 | Graphene oxide/polystyrene nano composite and preparation method thereof |
| CN102903531A (en) * | 2012-11-06 | 2013-01-30 | 东华大学 | Method for preparing composite electrode material of super capacitor |
| CN103285845A (en) * | 2013-05-20 | 2013-09-11 | 陕西科技大学 | Preparation method of graphene oxide wrapped titania microsphere photocatalyst |
| CN103334096A (en) * | 2013-07-02 | 2013-10-02 | 江苏大学 | Method for preparing nano-silver-graphene composite film |
| CN103545053A (en) * | 2013-10-25 | 2014-01-29 | 深圳市华星光电技术有限公司 | Preparation method of transparent conducting thin film and preparation method of CF substrate with conducting thin film |
| CN103639421A (en) * | 2013-12-04 | 2014-03-19 | 北京印刷学院 | Preparation method for high-conductivity graphene and silver nanoparticle composite materials |
Non-Patent Citations (1)
| Title |
|---|
| WENBING HU: "Graphene-Based Antibacterial Paper", 《ACS NANO》 * |
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| WO2016011905A1 (en) * | 2014-07-25 | 2016-01-28 | 中国科学院深圳先进技术研究院 | Silver-doped graphene composite paper and preparation method therefor |
| CN104891477A (en) * | 2015-05-15 | 2015-09-09 | 北京交通大学 | Simple and environment-friendly graphene paper preparation method |
| 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 |
| CN106865537A (en) * | 2017-03-17 | 2017-06-20 | 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 |
| CN111392717A (en) * | 2020-03-25 | 2020-07-10 | 宁波石墨烯创新中心有限公司 | Preparation method of concentrated graphene oxide solution and heat conducting film |
| CN112118708A (en) * | 2020-09-10 | 2020-12-22 | 安徽工业大学 | Heat-conducting film and preparation method thereof |
| CN112118708B (en) * | 2020-09-10 | 2023-03-21 | 安徽工业大学 | Heat-conducting film and preparation method thereof |
| CN113774725A (en) * | 2021-08-25 | 2021-12-10 | 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 |
| 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 |
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| Publication number | Publication date |
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| CN104163420B (en) | 2016-08-24 |
| WO2016011905A1 (en) | 2016-01-28 |
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