WO2016011905A1 - Silver-doped graphene composite paper and preparation method therefor - Google Patents

Silver-doped graphene composite paper and preparation method therefor Download PDF

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WO2016011905A1
WO2016011905A1 PCT/CN2015/084015 CN2015084015W WO2016011905A1 WO 2016011905 A1 WO2016011905 A1 WO 2016011905A1 CN 2015084015 W CN2015084015 W CN 2015084015W WO 2016011905 A1 WO2016011905 A1 WO 2016011905A1
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silver
composite paper
graphene oxide
doped graphene
preparing
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PCT/CN2015/084015
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French (fr)
Chinese (zh)
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孙蓉
黄胜云
符显珠
郭慧子
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中国科学院深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
    • 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

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  • the invention relates to the field of electronic packaging materials, in particular to silver-doped graphene composite paper and a preparation method thereof.
  • Graphene is a new material composed of a single layer of atoms, and its carbon atoms form a hexagonal honeycomb lattice with sp 2 hybrid orbitals. Graphene has long been considered a hypothetical structure and cannot be stably present alone. In 2004, the physicists of the University of Manchester, Andre Geim and Konstantin Novoselov, used tape to repeatedly bond the sheets from the graphite and finally successfully separated the graphene.
  • graphene Due to its special physical structure, graphene has a series of excellent properties: the world's thinnest and hardest nano material is almost completely transparent, absorbing only 2.3% of light; thermal conductivity is as high as 5300W/m ⁇ K, higher than carbon Nanotubes and diamonds; electron mobility at room temperature exceeds 15000 cm 2 /V ⁇ s, and is higher than carbon nanotubes or silicon crystals; and resistivity is only about 10 -6 ⁇ cm, lower than copper or silver, for the world The material with the lowest resistivity.
  • a silver-doped graphene composite paper prepared by the above-described method for preparing a silver-doped graphene composite paper is provided.
  • a method for preparing a silver-doped graphene composite paper comprising the following steps:
  • the mixture is subjected to evaporation treatment to obtain a silver-doped graphene oxide composite paper;
  • the silver-doped graphene oxide composite paper is placed in a solution containing a reducing agent for reduction treatment to obtain a silver-doped graphene composite paper.
  • the method for preparing graphene oxide is specifically:
  • the mixed liquid is transferred into a constant temperature water bath of 20 ° C to 40 ° C, and the reaction is stirred for 15 min to 180 min; deionized water is added to the mixed solution, and the reaction is carried out for 30 min to 60 min, and then the temperature of the constant temperature water bath of 20 ° C to 40 ° C is taken. It is raised to 80 ° C ⁇ 100 ° C, stirred for 30 min ⁇ 300 min; finally added hydrogen peroxide, the reaction is 30 min ⁇ 90 min, washed and dried to obtain graphene oxide.
  • the mass ratio of the silver nitrate to the graphene oxide is from 0.01 to 1:1 to 5.
  • the operation of evaporating the mixed liquid is specifically: evaporating at 30 ° C to 150 ° C for 0.5 hours to 24 hours.
  • the operation of evaporating the mixed solution is specifically: evaporating at 60 ° C to 100 ° C for 6 hours to 12 hours.
  • the reducing agent is selected from at least one of sodium borohydride, ascorbic acid, and hydrazine hydrate.
  • the solvent is at least one selected from the group consisting of methanol, ethanol, tetrahydrofuran, and dimethylformamide.
  • the concentration of the solution containing the reducing agent is from 0.01 mol/L to 5 mol/L.
  • the step of placing the silver-doped graphene oxide composite paper in a solution containing a reducing agent for reduction treatment is specifically: heating the solution containing the reducing agent to 30 ° C to 150
  • the silver-doped graphene oxide composite paper is placed in a solution containing a reducing agent at a temperature of 30 ° C to 150 ° C for 0.5 hour to 10 hours at ° C.
  • the preparation method of the above silver-doped graphene composite paper first prepares graphene oxide, prepares a graphene oxide suspension, and evaporates a mixture of graphene oxide suspension and silver nitrate to obtain silver-doped graphene oxide composite paper, which will
  • the silver-doped graphene oxide composite paper is subjected to a reduction treatment to obtain a silver-doped graphene composite paper.
  • the method has mild reaction conditions, low requirements on equipment and simple process.
  • it has been experimentally shown that the prepared silver-doped graphene composite paper has a high thermal conductivity in the vertical direction.
  • FIG. 1 is a flow chart showing a method of preparing a silver-doped graphene composite paper according to an embodiment
  • a method for preparing a silver-doped graphene composite paper includes the following steps S110 to S140 .
  • Step S110 preparing graphene oxide, and ultrasonically treating graphene oxide to prepare a graphene oxide suspension.
  • the method for preparing graphene oxide is specifically:
  • Step S210 uniformly mix the natural graphite and the sodium nitrate under ice water bath conditions, add concentrated sulfuric acid, stir for 10 min to 150 min, then add potassium permanganate, and continue stirring for 15 min to 150 min to obtain a mixed liquid.
  • Step S220 moving the mixed liquid into a constant temperature water bath of 20 ° C to 40 ° C, stirring the reaction for 15 min to 180 min; adding deionized water to the mixed solution, reacting for 30 min to 60 min, and then raising the temperature of the thermostatic water bath at 20 ° C to 40 ° C to 80 ° °C ⁇ 100 ° C, stirring reaction 30min ⁇ 300min; finally added hydrogen peroxide, reaction 30min ⁇ 90min, washing, drying to obtain graphene oxide.
  • the mass ratio of natural graphite, sodium nitrate and concentrated sulfuric acid is from 1 to 5 g:1 to 5 g:46 to 230 mL.
  • the mass ratio of natural graphite to potassium permanganate is from 1 to 5:6 to 30, preferably from 1 to 5:6 to 24.
  • the volume ratio of concentrated sulfuric acid, deionized water and hydrogen peroxide is from 46 to 230:92 to 460:40 to 200.
  • the concentrated sulfuric acid has a mass concentration of 95% to 98%, and the hydrogen peroxide has a mass concentration of 30%.
  • the stirring rate of both stirring operations is from 300 r/min to 1000 r/min, preferably from 300 r/min to 600 r/min.
  • the stirring rate of both stirring operations is from 300 r/min to 800 r/min, preferably from 300 r/min to 600 r/min.
  • the washing method is specifically: sequentially washing with hydrogen peroxide, hydrochloric acid and distilled water by centrifugation.
  • the hydrogen peroxide has a mass concentration of 30% and the hydrochloric acid has a mass concentration of 10%.
  • the centrifugal speed is from 500 r/min to 10000 r/min, and the centrifugation time is from 10 min to 60 min.
  • the drying method can be freeze-dried, air dried or vacuum dried.
  • the prepared graphene oxide was added to water and ultrasonicated to obtain a graphene oxide suspension.
  • the ultrasonic treatment has a power of 1000 W and a time of 1 h to 4 h.
  • the concentration of the graphene oxide suspension is from 0.5 g/L to 5 g/L.
  • Step S120 adding silver nitrate to the graphene oxide suspension to obtain a mixed liquid.
  • the mass ratio of silver nitrate to graphene oxide is from 0.01 to 1:1 to 5, preferably from 0.1 to 0.5:2 to 3.
  • Oxidation Silver nitrate was added to the graphene suspension, and the mixture was stirred at 300 r/min for 0.5 hour to 2 hours, and uniformly mixed to obtain a mixed solution.
  • Step S130 The mixed solution is subjected to evaporation treatment to obtain a silver-doped graphene oxide composite paper.
  • the mixture was subjected to evaporation treatment to evaporate the solvent, and silver was doped into the graphene oxide.
  • the operation of the evaporation treatment is specifically: the mixture is placed in a blast drying oven and evaporated at 30 ° C to 150 ° C for 0.5 hours to 24 hours.
  • the temperature of the evaporation treatment is from 60 ° C to 100 ° C for a period of from 6 hours to 12 hours.
  • Step S140 The silver-doped graphene oxide composite paper is placed in a solution containing a reducing agent for reduction treatment to obtain a silver-doped graphene composite paper.
  • the reducing agent is selected from at least one of sodium borohydride, ascorbic acid and hydrazine hydrate.
  • the solvent is at least one selected from the group consisting of methanol, ethanol, tetrahydrofuran, and dimethylformamide.
  • the concentration of the solution containing the reducing agent is from 0.01 mol/L to 5 mol/L, more preferably from 0.05 mol/L to 1 mol/L.
  • the step of placing the silver-doped graphene oxide composite paper in a solution containing a reducing agent for reduction treatment is specifically: heating the solution containing the reducing agent to 30 ° C to 150 ° C, and placing the silver-doped graphene oxide composite paper
  • the reaction is carried out in a solution containing a reducing agent at a temperature of from 30 ° C to 150 ° C for from 0.5 hours to 10 hours, preferably from 0.5 hours to 5 hours.
  • the temperature of the solution containing the reducing agent during the reduction is from 40 ° C to 100 ° C.
  • the preparation method of the above silver-doped graphene composite paper first prepares graphene oxide, prepares a graphene oxide suspension, and evaporates a mixture of graphene oxide suspension and silver nitrate to obtain silver-doped graphene oxide composite paper, The silver-doped graphene oxide composite paper is subjected to a reduction treatment to obtain a silver-doped graphene composite paper.
  • the method has mild reaction conditions, low requirements on equipment, simple process and easy industrialization.
  • the prepared silver-doped graphene composite paper has a high thermal conductivity in the vertical direction.
  • the preparation method of the silver-doped graphene composite paper can prepare a silver-doped graphene composite paper having a thickness of 0.5 ⁇ m to 2 mm, and the thermal conductivity in the plane direction is 200-700 W/mK, and the thermal conductivity in the vertical direction is 2-5. W/mK, the square resistance is 1 to 200 ⁇ / ⁇ .
  • This performance of silver-doped graphene composite paper can be widely used in the field of electronic packaging.
  • Thermal conductivity measured by the thermal resistance and thermal conductivity measuring device of the interface material designed and manufactured according to ASTM D 5470-06, the model number is LW-9389;
  • the reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide.
  • the rate of centrifugal cleaning was 500 r/min for 60 min.
  • 0.5 g of graphene oxide powder was weighed, 1 L of deionized water was added, sonicated for 60 min, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 0.5 g/L was obtained.
  • 0.1 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 60 minutes to obtain a mixed solution.
  • the mixture was again subjected to evaporation treatment in a blast drying oven at 80 ° C for 12 hours to obtain a silver-doped graphene oxide composite paper.
  • the silver-doped graphene oxide composite paper was immersed in an ethanol solution of sodium borohydride having a molar concentration of 0.5 mol/L for chemical reduction, the reaction temperature was 150 ° C, and the reaction time was 0.5 hours to obtain a silver-doped graphene composite paper. .
  • a 55 ⁇ m thick silver-doped graphene composite paper was prepared by the above method, and the horizontal thermal conductivity was 200 W/mK, the vertical thermal conductivity was 2.7 W/mK, and the square resistance was 109 ⁇ / ⁇ .
  • Example 2 is an SEM image of the silver-doped graphene composite paper prepared in Example 1. As can be seen from FIG. 2, a plurality of silver-doped graphene composite papers were prepared in the present Example 1.
  • the reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water, and dried to obtain graphene oxide.
  • the rate of centrifugal cleaning was 10,000 r/min for 10 minutes.
  • 2.5 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 4 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 5 g/L was obtained.
  • 0.5 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 2 hours to obtain a mixed solution.
  • the mixture was again subjected to evaporation treatment in a blast drying oven at 90 ° C for 10 hours to obtain a silver-doped graphene oxide composite paper.
  • the silver-doped graphene oxide composite paper was immersed in an ethanol solution of ascorbic acid having a molar concentration of 1 mol/L for chemical reduction, the reaction temperature was 60 ° C, and the reaction time was 2 hours to obtain a silver-doped graphene composite paper.
  • a 25 ⁇ m thick silver-doped graphene paper can be prepared by the above method, and the horizontal thermal conductivity is 700 W/mK, the vertical thermal conductivity is 3.5 W/mK, and the square resistance is 25 ⁇ / ⁇ .
  • the reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide, and the rate of centrifugal cleaning was obtained. It is 5000r/min and the time is 30min. 2 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 4 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 4 g/L was obtained. 0.5 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 2 hours to obtain a mixed solution.
  • a 40 ⁇ m thick silver-doped graphene paper can be prepared by the above method, and the horizontal thermal conductivity is 570 W/mK, the vertical thermal conductivity is 3.2 W/mK, and the square resistance is 70 ⁇ / ⁇ .
  • the reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide, and the rate of centrifugal cleaning was 1000 r/min for 45 minutes.
  • 1 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 2 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 1 g/L was obtained.
  • 0.01 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 30 minutes to obtain a mixed solution.
  • the mixture was placed in a blast drying oven at 30 ° C for evaporation for 12 hours to obtain a silver-doped graphene oxide composite paper.
  • the silver-doped graphene oxide composite paper was immersed in a methanol solution of sodium borohydride having a molar concentration of 5 mol/L for chemical reduction, the reaction temperature was 100 ° C, and the reaction time was 5 hours to obtain a silver-doped graphene composite paper.
  • a 30 ⁇ m thick silver-doped graphene paper can be prepared by the above method, and the horizontal thermal conductivity is 602 W/mK, the vertical thermal conductivity is 3.3 W/mK, and the square resistance is 65 ⁇ / ⁇ .
  • the reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide.
  • the rate of centrifugal cleaning was 2000 r/min, and the time was 30 min.
  • 1 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 2 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 1 g/L was obtained.
  • 0.01 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 30 minutes to obtain a mixed solution.
  • the mixture was placed in a blast drying oven at 30 ° C for evaporation for 12 hours to obtain a silver-doped graphene oxide composite paper.
  • the silver-doped graphene oxide composite paper is immersed in a solution containing a reducing agent at a molar concentration of 5 mol/L for chemical reduction, and in the solution containing the reducing agent, the reducing agent is ascorbic acid and hydrazine hydrate in a mass ratio of 1:1.
  • the solvent was tetrahydrofuran and dimethylformamide in a volume ratio of 1:1.
  • the reaction temperature was 40 ° C and the reaction time was 5 hours to obtain a silver-doped graphene composite paper.
  • a 30 ⁇ m thick silver-doped graphene paper was prepared by the above method, and the horizontal thermal conductivity was 479 W/mK, the vertical thermal conductivity was 3.1 W/mK, and the square resistance was 73 ⁇ / ⁇ .

Abstract

The present invention relates to silver-doped graphene composite paper and a preparation method therefor. The preparation method for the silver-doped graphene composite paper comprises the steps of: preparing graphene oxide, and carrying out ultrasonic treatment on graphene oxide to prepare a graphene oxide suspension; adding silver nitrate into the graphene oxide suspension to obtain a mixed liquid; evaporating the mixed liquid to obtain silver-doped graphene oxide composite paper; and carrying out 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. Compared with a vacuum filtration method, the method provided by the present invention has mild reaction conditions, 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

银掺杂石墨烯复合纸及其制备方法Silver doped graphene composite paper and preparation method thereof 技术领域Technical field
本发明涉及电子封装材料领域，特别是涉及银掺杂石墨烯复合纸及其制备方法。The invention relates to the field of electronic packaging materials, in particular to silver-doped graphene composite paper and a preparation method thereof.
背景技术Background technique
随着电子器件向高集成、高运算领域发展，散热成为一个难题。一直以来，铜、银等传统散热材料被广泛应用于电子器件和产品散热。但是铜、银材料价格昂贵，易被氧化，密度高，热膨胀系数大，而碳材料由于高导热、低密度、低热膨胀系数且储量丰富、价格低廉等一系列优异特性而逐渐兴起。研究表明普通碳纳米管的导热系数为3000～3500W/m·K，金刚石为1000～2200W/m·K，而单层石墨烯的导热系数更是高达5300W/m·K。As electronic devices move toward high integration and high computing, heat dissipation becomes a problem. Traditional heat sink materials such as copper and silver have been widely used in electronic devices and products for heat dissipation. However, copper and silver materials are expensive, easily oxidized, have high density, and have a large coefficient of thermal expansion, and carbon materials are gradually emerging due to a series of excellent characteristics such as high thermal conductivity, low density, low thermal expansion coefficient, abundant reserves, and low price. Studies have shown that the thermal conductivity of ordinary carbon nanotubes is 3000 ~ 3500W / m · K, diamond is 1000 ~ 2200W / m · K, and the thermal conductivity of single-layer graphene is as high as 5300W / m · K.
石墨烯是单层原子构成的新材料，其碳原子以sp2杂化轨道组成六角蜂巢晶格。一直以来，石墨烯被认为是假设性的结构，无法单独稳定存在。2004年，英国曼彻斯特大学物理学家Andre Geim和Konstantin Novoselov利用胶带从石墨上反复粘下薄片，最终成功地分离出石墨烯。石墨烯由于其特殊的物理结构，具有一系列优异特性：世上最薄、最坚硬的纳米材料，几乎是完全透明的，只吸收2.3％的光；导热系数高达5300W/m·K，高于碳纳米管和金刚石；常温下其电子迁移率超过15000cm2/V·s，又比纳米碳管或硅晶体高；而电阻率只约10-6Ω·cm，比铜或银更低，为世上电阻率最小的材料。中国科学院山西煤炭化学研究所的孔庆强等利用真空抽滤将短切碳纤维与氧化石墨烯制备成复合纸，再通过高温热退火获得石墨烯复合纸，其水平面内的导热率高达977W/mK，但是垂直方向的导热率只有0.38W/mK。而且真空抽滤获得的产品面积小，高温热退火耗能大，不适合工业化生产，需要寻找一种简单易行的方法，实现大规模生产，且获得的产品垂直方向的热传导率要有较大幅度的提升。 Graphene is a new material composed of a single layer of atoms, and its carbon atoms form a hexagonal honeycomb lattice with sp 2 hybrid orbitals. Graphene has long been considered a hypothetical structure and cannot be stably present alone. In 2004, the physicists of the University of Manchester, Andre Geim and Konstantin Novoselov, used tape to repeatedly bond the sheets from the graphite and finally successfully separated the graphene. Due to its special physical structure, graphene has a series of excellent properties: the world's thinnest and hardest nano material is almost completely transparent, absorbing only 2.3% of light; thermal conductivity is as high as 5300W/m·K, higher than carbon Nanotubes and diamonds; electron mobility at room temperature exceeds 15000 cm 2 /V·s, and is higher than carbon nanotubes or silicon crystals; and resistivity is only about 10 -6 Ω·cm, lower than copper or silver, for the world The material with the lowest resistivity. Kong Qingqiang, from the Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, used vacuum filtration to prepare chopped carbon fibers and graphene oxide into composite paper, and then obtained high temperature thermal annealing to obtain graphene composite paper with a thermal conductivity of 977 W/mK in the horizontal plane, but The thermal conductivity in the vertical direction is only 0.38 W/mK. Moreover, the product obtained by vacuum filtration has a small area, and the high-temperature thermal annealing consumes a large amount of energy, which is not suitable for industrial production. It is necessary to find a simple and easy method to achieve large-scale production, and the obtained product has a large thermal conductivity in the vertical direction. Increase in range.
发明内容Summary of the invention
基于此，有必要提供一种工艺简单的银掺杂石墨烯复合纸，以制备垂直方向的导热率较高的银掺杂石墨烯复合纸。Based on this, it is necessary to provide a silver-doped graphene composite paper with a simple process to prepare a silver-doped graphene composite paper having a high thermal conductivity in the vertical direction.
进一步，提供一种由上述银掺杂石墨烯复合纸的制备方法制备得到的银掺杂石墨烯复合纸。Further, a silver-doped graphene composite paper prepared by the above-described method for preparing a silver-doped graphene composite paper is provided.
一种银掺杂石墨烯复合纸的制备方法，包括如下步骤：A method for preparing a silver-doped graphene composite paper, comprising the following steps:
制备氧化石墨烯，将所述氧化石墨烯进行超声处理，制备得到氧化石墨烯悬浮液；Preparing graphene oxide, sonicating the graphene oxide to prepare a graphene oxide suspension;
向所述氧化石墨烯悬浮液中加入硝酸银得到混合液；Adding silver nitrate to the graphene oxide suspension to obtain a mixed liquid;
将所述混合液进行蒸发处理，得到银掺杂氧化石墨烯复合纸；及The mixture is subjected to evaporation treatment to obtain a silver-doped graphene oxide composite paper;
将所述银掺杂氧化石墨烯复合纸放入含有还原剂的溶液中进行还原处理，得到银掺杂石墨烯复合纸。The silver-doped graphene oxide composite paper is placed in a solution containing a reducing agent for reduction treatment to obtain a silver-doped graphene composite paper.
在其中一个实施例中，所述制备氧化石墨烯的方法具体为：In one embodiment, the method for preparing graphene oxide is specifically:
在冰水浴条件下，将天然石墨和硝酸钠混合均匀，加入浓硫酸，搅拌10min～150min，然后加入高锰酸钾，继续搅拌10min～150min，得到混合液；Under the condition of ice water bath, the natural graphite and sodium nitrate are uniformly mixed, concentrated sulfuric acid is added, stirred for 10 min to 150 min, then potassium permanganate is added, and stirring is continued for 10 min to 150 min to obtain a mixed liquid;
将所述混合液移入20℃～40℃恒温水浴中，搅拌反应15min～180min；向所述混合液中加入去离子水，反应30min～60min，然后将所述20℃～40℃恒温水浴的温度升至80℃～100℃，搅拌30min～300min；最后加入双氧水，反应30min～90min，洗涤、干燥得到氧化石墨烯。The mixed liquid is transferred into a constant temperature water bath of 20 ° C to 40 ° C, and the reaction is stirred for 15 min to 180 min; deionized water is added to the mixed solution, and the reaction is carried out for 30 min to 60 min, and then the temperature of the constant temperature water bath of 20 ° C to 40 ° C is taken. It is raised to 80 ° C ~ 100 ° C, stirred for 30 min ~ 300 min; finally added hydrogen peroxide, the reaction is 30 min ~ 90 min, washed and dried to obtain graphene oxide.
在其中一个实施例中，所述硝酸银与所述氧化石墨烯的质量比为0.01～1∶1～5。In one embodiment, the mass ratio of the silver nitrate to the graphene oxide is from 0.01 to 1:1 to 5.
在其中一个实施例中，所述将所述混合液进行蒸发处理的操作具体为：于30℃～150℃下蒸发0.5小时～24小时。In one embodiment, the operation of evaporating the mixed liquid is specifically: evaporating at 30 ° C to 150 ° C for 0.5 hours to 24 hours.
在其中一个实施例中，所述将所述混合液进行蒸发处理的操作具体为：于60℃～100℃下蒸发6小时～12小时。In one embodiment, the operation of evaporating the mixed solution is specifically: evaporating at 60 ° C to 100 ° C for 6 hours to 12 hours.
在其中一个实施例中，所述还原剂选自硼氢化钠、抗坏血酸及水合肼中的至少一种。 In one embodiment, the reducing agent is selected from at least one of sodium borohydride, ascorbic acid, and hydrazine hydrate.
在其中一个实施例中，所述含有还原剂的溶液中，溶剂选自甲醇、乙醇、四氢呋喃及二甲基甲酰胺中的至少一种。In one embodiment, in the solution containing the reducing agent, the solvent is at least one selected from the group consisting of methanol, ethanol, tetrahydrofuran, and dimethylformamide.
在其中一个实施例中，所述含有还原剂的溶液的浓度为0.01mol/L～5mol/L。In one embodiment, the concentration of the solution containing the reducing agent is from 0.01 mol/L to 5 mol/L.
在其中一个实施例中，所述将所述银掺杂氧化石墨烯复合纸放入含有还原剂的溶液中进行还原处理的步骤具体为：将所述含有还原剂的溶液加热至30℃～150℃，将所述银掺杂氧化石墨烯复合纸放入温度为30℃～150℃的含有还原剂的溶液中反应0.5小时～10小时。In one embodiment, the step of placing the silver-doped graphene oxide composite paper in a solution containing a reducing agent for reduction treatment is specifically: heating the solution containing the reducing agent to 30 ° C to 150 The silver-doped graphene oxide composite paper is placed in a solution containing a reducing agent at a temperature of 30 ° C to 150 ° C for 0.5 hour to 10 hours at ° C.
一种上述银掺杂石墨烯复合纸的制备方法制备的银掺杂石墨烯复合纸。A silver-doped graphene composite paper prepared by the above method for preparing silver-doped graphene composite paper.
上述银掺杂石墨烯复合纸的制备方法先制备氧化石墨烯，再制备氧化石墨烯悬浮液，蒸发处理氧化石墨烯悬浮液和硝酸银的混合液，得到银掺杂氧化石墨烯复合纸，将该银掺杂氧化石墨烯复合纸进行还原处理即得到银掺杂石墨烯复合纸。该方法相对于真空抽滤法，反应条件温和，对设备要求低，工艺简单。并且，经实验表明，所制备得到的银掺杂石墨烯复合纸的垂直方向的热导率较高。The preparation method of the above silver-doped graphene composite paper first prepares graphene oxide, prepares a graphene oxide suspension, and evaporates a mixture of graphene oxide suspension and silver nitrate to obtain silver-doped graphene oxide composite paper, which will The silver-doped graphene oxide composite paper is subjected to a reduction treatment to obtain a silver-doped graphene composite paper. Compared with the vacuum filtration method, the method has mild reaction conditions, low requirements on equipment and simple process. Moreover, it has been experimentally shown that the prepared silver-doped graphene composite paper has a high thermal conductivity in the vertical direction.
附图说明DRAWINGS
图1为一实施方式的银掺杂石墨烯复合纸的制备方法的流程图；1 is a flow chart showing a method of preparing a silver-doped graphene composite paper according to an embodiment;
图2为实施例1的银掺杂石墨烯复合纸的SEM图。2 is an SEM image of the silver-doped graphene composite paper of Example 1.
具体实施方式detailed description
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。The above described objects, features and advantages of the present invention will become more apparent from the aspects of the appended claims. Numerous specific details are set forth in the description below in order to provide a thorough understanding of the invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the invention, and thus the invention is not limited by the specific embodiments disclosed below.
请参阅图1，一实施方式的银掺杂石墨烯复合纸的制备方法，包括如下步骤S110～步骤S140。 Referring to FIG. 1 , a method for preparing a silver-doped graphene composite paper according to an embodiment includes the following steps S110 to S140 .
步骤S110：制备氧化石墨烯，将氧化石墨烯进行超声处理，制备得到氧化石墨烯悬浮液。Step S110: preparing graphene oxide, and ultrasonically treating graphene oxide to prepare a graphene oxide suspension.
制备氧化石墨烯的方法具体为：The method for preparing graphene oxide is specifically:
步骤S210：在冰水浴条件下，将天然石墨和硝酸钠混合物均匀，加入浓硫酸，搅拌10min～150min，然后加入高锰酸钾，继续搅拌15min～150min，得到混合液。Step S210: uniformly mix the natural graphite and the sodium nitrate under ice water bath conditions, add concentrated sulfuric acid, stir for 10 min to 150 min, then add potassium permanganate, and continue stirring for 15 min to 150 min to obtain a mixed liquid.
步骤S220：将混合液移入20℃～40℃恒温水浴中，搅拌反应15min～180min；向混合液中加入去离子水，反应30min～60min，然后将20℃～40℃恒温水浴的温度升至80℃～100℃，搅拌反应30min～300min；最后加入双氧水，反应30min～90min，洗涤、干燥得到氧化石墨烯。Step S220: moving the mixed liquid into a constant temperature water bath of 20 ° C to 40 ° C, stirring the reaction for 15 min to 180 min; adding deionized water to the mixed solution, reacting for 30 min to 60 min, and then raising the temperature of the thermostatic water bath at 20 ° C to 40 ° C to 80 ° °C ~ 100 ° C, stirring reaction 30min ~ 300min; finally added hydrogen peroxide, reaction 30min ~ 90min, washing, drying to obtain graphene oxide.
优选地，天然石墨、硝酸钠和浓硫酸的质量体积比为1～5g∶1～5g∶46～230mL。天然石墨与高锰酸钾的质量比为1～5∶6～30，优选为1～5∶6～24。Preferably, the mass ratio of natural graphite, sodium nitrate and concentrated sulfuric acid is from 1 to 5 g:1 to 5 g:46 to 230 mL. The mass ratio of natural graphite to potassium permanganate is from 1 to 5:6 to 30, preferably from 1 to 5:6 to 24.
优选地，浓硫酸、去离子水和双氧水的体积比为46～230∶92～460∶40～200。Preferably, the volume ratio of concentrated sulfuric acid, deionized water and hydrogen peroxide is from 46 to 230:92 to 460:40 to 200.
进一步优选地，浓硫酸的质量浓度为95％～98％，双氧水的质量浓度为30％。Further preferably, the concentrated sulfuric acid has a mass concentration of 95% to 98%, and the hydrogen peroxide has a mass concentration of 30%.
步骤S210中，两个搅拌操作的搅拌速率均为300r/min～1000r/min，优选为300r/min～600r/min。In step S210, the stirring rate of both stirring operations is from 300 r/min to 1000 r/min, preferably from 300 r/min to 600 r/min.
步骤S220中，两个搅拌操作的搅拌速率均为300r/min～800r/min，优选为300r/min～600r/min。In step S220, the stirring rate of both stirring operations is from 300 r/min to 800 r/min, preferably from 300 r/min to 600 r/min.
洗涤的方法具体为：依次用双氧水、盐酸和蒸馏水离心清洗。优选地，双氧水的质量浓度为30％，盐酸的质量浓度为10％。离心的转速为500r/min～10000r/min，离心的时间为10min～60min。The washing method is specifically: sequentially washing with hydrogen peroxide, hydrochloric acid and distilled water by centrifugation. Preferably, the hydrogen peroxide has a mass concentration of 30% and the hydrochloric acid has a mass concentration of 10%. The centrifugal speed is from 500 r/min to 10000 r/min, and the centrifugation time is from 10 min to 60 min.
干燥的方法可以冷冻干燥、鼓风干燥或真空干燥。The drying method can be freeze-dried, air dried or vacuum dried.
将制备得到的氧化石墨烯加入水中，进行超声处理，得到氧化石墨烯悬浮液。优选地，超声处理的功率为1000W，时间为1h～4h。The prepared graphene oxide was added to water and ultrasonicated to obtain a graphene oxide suspension. Preferably, the ultrasonic treatment has a power of 1000 W and a time of 1 h to 4 h.
优选地，氧化石墨烯悬浮液的浓度为0.5g/L～5g/L。Preferably, the concentration of the graphene oxide suspension is from 0.5 g/L to 5 g/L.
步骤S120：向氧化石墨烯悬浮液中加入硝酸银得到混合液。Step S120: adding silver nitrate to the graphene oxide suspension to obtain a mixed liquid.
硝酸银与氧化石墨烯的质量比为0.01～1∶1～5，优选为0.1～0.5∶2～3。向氧化 石墨烯悬浮液中加入硝酸银，在300r/min下搅拌0.5小时～2小时，混合均匀，得到混合液。The mass ratio of silver nitrate to graphene oxide is from 0.01 to 1:1 to 5, preferably from 0.1 to 0.5:2 to 3. Oxidation Silver nitrate was added to the graphene suspension, and the mixture was stirred at 300 r/min for 0.5 hour to 2 hours, and uniformly mixed to obtain a mixed solution.
步骤S130：将混合液进行蒸发处理，得到银掺杂氧化石墨烯复合纸。Step S130: The mixed solution is subjected to evaporation treatment to obtain a silver-doped graphene oxide composite paper.
将混合液进行蒸发处理，以蒸干溶剂，并使银掺杂于氧化石墨烯中。蒸发处理的操作具体为：将混合液放入鼓风干燥箱中，于30℃～150℃下蒸发0.5小时～24小时。The mixture was subjected to evaporation treatment to evaporate the solvent, and silver was doped into the graphene oxide. The operation of the evaporation treatment is specifically: the mixture is placed in a blast drying oven and evaporated at 30 ° C to 150 ° C for 0.5 hours to 24 hours.
优选地，蒸发处理的温度为60℃～100℃，时间为6小时～12小时。Preferably, the temperature of the evaporation treatment is from 60 ° C to 100 ° C for a period of from 6 hours to 12 hours.
步骤S140：将银掺杂氧化石墨烯复合纸放入含有还原剂的溶液中进行还原处理，得到银掺杂石墨烯复合纸。Step S140: The silver-doped graphene oxide composite paper is placed in a solution containing a reducing agent for reduction treatment to obtain a silver-doped graphene composite paper.
优选地，还原剂选自硼氢化钠、抗坏血酸及水合肼中的至少一种。Preferably, the reducing agent is selected from at least one of sodium borohydride, ascorbic acid and hydrazine hydrate.
含有还原剂的溶液中，溶剂选自甲醇、乙醇、四氢呋喃及二甲基甲酰胺中的至少一种。In the solution containing a reducing agent, the solvent is at least one selected from the group consisting of methanol, ethanol, tetrahydrofuran, and dimethylformamide.
进一步优选地，含有还原剂的溶液的浓度为0.01mol/L～5mol/L，更优选为0.05mol/L～1mol/L。Further preferably, the concentration of the solution containing the reducing agent is from 0.01 mol/L to 5 mol/L, more preferably from 0.05 mol/L to 1 mol/L.
将银掺杂氧化石墨烯复合纸放入含有还原剂的溶液中进行还原处理的步骤具体为：将含有还原剂的溶液加热至30℃～150℃，将银掺杂氧化石墨烯复合纸放入温度为30℃～150℃的含有还原剂的溶液中反应0.5小时～10小时，优选为0.5小时～5小时。The step of placing the silver-doped graphene oxide composite paper in a solution containing a reducing agent for reduction treatment is specifically: heating the solution containing the reducing agent to 30 ° C to 150 ° C, and placing the silver-doped graphene oxide composite paper The reaction is carried out in a solution containing a reducing agent at a temperature of from 30 ° C to 150 ° C for from 0.5 hours to 10 hours, preferably from 0.5 hours to 5 hours.
优选地，还原过程中，含有还原剂的溶液的温度为40℃～100℃。Preferably, the temperature of the solution containing the reducing agent during the reduction is from 40 ° C to 100 ° C.
上述银掺杂石墨烯复合纸的制备方法先制备氧化石墨烯，再配制氧化石墨烯悬浮液，蒸发处理氧化石墨烯悬浮液和硝酸银的混合液，得到银掺杂氧化石墨烯复合纸，将该银掺杂氧化石墨烯复合纸进行还原处理即得到银掺杂石墨烯复合纸。该方法相对于真空抽滤法反应条件温和，对设备要求低，工艺简单，易实现工业化。并且，经实验表明，所制备得到的银掺杂石墨烯复合纸的垂直方向的热导率较高。The preparation method of the above silver-doped graphene composite paper first prepares graphene oxide, prepares a graphene oxide suspension, and evaporates a mixture of graphene oxide suspension and silver nitrate to obtain silver-doped graphene oxide composite paper, The silver-doped graphene oxide composite paper is subjected to a reduction treatment to obtain a silver-doped graphene composite paper. Compared with the vacuum filtration method, the method has mild reaction conditions, low requirements on equipment, simple process and easy industrialization. Moreover, it has been experimentally shown that the prepared silver-doped graphene composite paper has a high thermal conductivity in the vertical direction.
上述银掺杂石墨烯复合纸的制备方法能够制备厚度为0.5μm～2mm的银掺杂石墨烯复合纸，其平面方向导热率为200～700W/mK，垂直方向导热率为2～5 W/mK，方阻为1～200Ω/□。该性能的银掺杂石墨烯复合纸能够广泛应用于电子封装领域。The preparation method of the silver-doped graphene composite paper can prepare a silver-doped graphene composite paper having a thickness of 0.5 μm to 2 mm, and the thermal conductivity in the plane direction is 200-700 W/mK, and the thermal conductivity in the vertical direction is 2-5. W/mK, the square resistance is 1 to 200 Ω / □. This performance of silver-doped graphene composite paper can be widely used in the field of electronic packaging.
以下通过具体实施例进一步阐述。The following is further illustrated by specific examples.
以下实施例中的测定方法如下：The measurement methods in the following examples are as follows:
(1)导热率：采用ASTM D 5470-06规范设计制造的界面材料热阻及热传导系数量测装置进行测定，其型号为LW-9389；(1) Thermal conductivity: measured by the thermal resistance and thermal conductivity measuring device of the interface material designed and manufactured according to ASTM D 5470-06, the model number is LW-9389;
(2)方阻测试：采用美国公司生产的四探针表面电阻测试仪，其型号为PRO4-6000。(2) Square resistance test: The four-probe surface resistance tester produced by American company was used, and its model was PRO4-6000.
实施例1Example 1
在冰水浴条件下，将1g天然石墨与1g硝酸钠混合均匀，再加入46ml的浓硫酸，在1000r/min条件下搅拌10min；加入6g高锰酸钾，在600r/min条件下搅拌30min得到混合液；将上述混合液移入35℃水浴中，搅拌反应60min；再加入92mL的去离子水，反应30min，将35℃的水浴升温至98℃，搅拌反应60min；最后加入40mL质量浓度为30％的双氧水，继续反应30min直到溶液变为亮黄色。将反应完全的混合溶液依次用质量浓度为30％的双氧水、质量浓度为10％的盐酸和蒸馏水进行离心清洗并干燥，获得氧化石墨烯，离心清洗的速率为500r/min，时间为60min。称取氧化石墨烯粉末0.5g，加入1L去离子水，超声处理60min，功率为1000W，获得质量浓度为0.5g/L的氧化石墨烯悬浮液。向氧化石墨烯悬浮液中加入0.1g硝酸银，在300r/min条件下搅拌60min，得到混合液。再将混合液置于80℃的鼓风干燥箱中进行蒸发处理12小时，获得银掺杂氧化石墨烯复合纸。最后将银掺杂氧化石墨烯复合纸浸入摩尔浓度为0.5mol/L的硼氢化钠的乙醇溶液中进行化学还原，反应温度为150℃，反应时间为0.5小时，获得银掺杂石墨烯复合纸。通过上述方法可制备得到55μm厚的银掺杂石墨烯复合纸，水平方向热导率为200W/mK，垂直热导率为2.7W/mK，方阻为109Ω/□。In an ice water bath, 1 g of natural graphite and 1 g of sodium nitrate were uniformly mixed, and then 46 ml of concentrated sulfuric acid was added, and stirred at 1000 r/min for 10 min; 6 g of potassium permanganate was added, and the mixture was stirred at 600 r/min for 30 min to obtain a mixture. The mixture was transferred to a 35 ° C water bath, stirred for 60 min; then added 92 mL of deionized water, reacted for 30 min, the 35 ° C water bath was heated to 98 ° C, stirred for 60 min; finally added 40 mL of mass concentration of 30% Hydrogen peroxide, continue to react for 30 min until the solution turns bright yellow. The reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide. The rate of centrifugal cleaning was 500 r/min for 60 min. 0.5 g of graphene oxide powder was weighed, 1 L of deionized water was added, sonicated for 60 min, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 0.5 g/L was obtained. 0.1 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 60 minutes to obtain a mixed solution. The mixture was again subjected to evaporation treatment in a blast drying oven at 80 ° C for 12 hours to obtain a silver-doped graphene oxide composite paper. Finally, the silver-doped graphene oxide composite paper was immersed in an ethanol solution of sodium borohydride having a molar concentration of 0.5 mol/L for chemical reduction, the reaction temperature was 150 ° C, and the reaction time was 0.5 hours to obtain a silver-doped graphene composite paper. . A 55 μm thick silver-doped graphene composite paper was prepared by the above method, and the horizontal thermal conductivity was 200 W/mK, the vertical thermal conductivity was 2.7 W/mK, and the square resistance was 109 Ω/□.
图2为本实施例1制备的银掺杂石墨烯复合纸的SEM图，由图2可看出，本实施例1制备得到多个银掺杂石墨烯复合纸。 2 is an SEM image of the silver-doped graphene composite paper prepared in Example 1. As can be seen from FIG. 2, a plurality of silver-doped graphene composite papers were prepared in the present Example 1.
实施例2Example 2
在冰水浴条件下，将1g天然石墨与1g硝酸钠混合均匀，再加入46ml的浓硫酸，在300r/min条件下搅拌150min；加入6g高锰酸钾，在300r/min条件下搅拌60min得到混合液；将上述混合液移入20℃水浴中，搅拌反应180min；再加入92mL的去离子水，反应30min，将20℃的水浴升温至98℃，搅拌反应120min；最后加入40mL质量浓度为30％的双氧水，继续反应30min直到溶液变为亮黄色。将反应完全的混合溶液进行依次用质量浓度为30％的双氧水、质量浓度为10％的盐酸和蒸馏水进行离心清洗并干燥，获得氧化石墨烯，离心清洗的速率为10000r/min，时间为10min。称取氧化石墨烯粉末2.5g，加入0.5L去离子水，超声处理4h，功率为1000W，获得质量浓度为5g/L的氧化石墨烯悬浮液。向氧化石墨烯悬浮液中加入0.5g硝酸银，在300r/min条件下搅拌2h，得到混合液。再将混合液置于90℃的鼓风干燥箱中进行蒸发处理10小时，获得银掺杂氧化石墨烯复合纸。最后将银掺杂氧化石墨烯复合纸浸入摩尔浓度为1mol/L的抗坏血酸的乙醇溶液中进行化学还原，反应温度为60℃，反应时间为2小时，获得银掺杂石墨烯复合纸。通过上述方法可制备得到25μm厚的银掺杂石墨烯纸，水平方向热导率为700W/mK，垂直热导率为3.5W/mK，方阻为25Ω/□。In an ice water bath condition, 1 g of natural graphite and 1 g of sodium nitrate were uniformly mixed, and then 46 ml of concentrated sulfuric acid was added, and stirred at 300 r/min for 150 min; 6 g of potassium permanganate was added, and the mixture was stirred at 300 r/min for 60 min to obtain a mixture. The solution was transferred to a 20 ° C water bath, stirred for 180 min; then added 92 mL of deionized water, reacted for 30 min, the water bath at 20 ° C was heated to 98 ° C, stirred for 120 min; finally added 40 mL of mass concentration of 30% Hydrogen peroxide, continue to react for 30 min until the solution turns bright yellow. The reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water, and dried to obtain graphene oxide. The rate of centrifugal cleaning was 10,000 r/min for 10 minutes. 2.5 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 4 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 5 g/L was obtained. 0.5 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 2 hours to obtain a mixed solution. The mixture was again subjected to evaporation treatment in a blast drying oven at 90 ° C for 10 hours to obtain a silver-doped graphene oxide composite paper. Finally, the silver-doped graphene oxide composite paper was immersed in an ethanol solution of ascorbic acid having a molar concentration of 1 mol/L for chemical reduction, the reaction temperature was 60 ° C, and the reaction time was 2 hours to obtain a silver-doped graphene composite paper. A 25 μm thick silver-doped graphene paper can be prepared by the above method, and the horizontal thermal conductivity is 700 W/mK, the vertical thermal conductivity is 3.5 W/mK, and the square resistance is 25 Ω/□.
实施例3Example 3
在冰水浴条件下，将2g天然石墨与4g硝酸钠混合均匀，再加入182ml的浓硫酸，在800r/min条件下搅拌15min；加入18g高锰酸钾，在800r/min条件下搅拌15min得到混合液；将上述混合液移入40℃水浴中，搅拌反应15min；再加入182mL的去离子水，反应60min，将40℃的水浴升温至80℃，搅拌反应300min；加入80mL质量浓度为30％的双氧水，继续反应90min直到溶液变为亮黄色。将反应完全的混合溶液依次用质量浓度为30％的双氧水、质量浓度为10％的盐酸和蒸馏水进行离心清洗并干燥，获得氧化石墨烯，离心清洗的速率 为5000r/min，时间为30min。称取氧化石墨烯粉末2g，加入0.5L去离子水，超声处理4h，功率为1000W，获得质量浓度为4g/L的氧化石墨烯悬浮液。向氧化石墨烯悬浮液中加入0.5g硝酸银，在300r/min条件下搅拌2h，得到混合液。再将混合液置于100℃的鼓风干燥箱中进行蒸发处理6小时，获得银掺杂氧化石墨烯复合纸。最后将银掺杂氧化石墨烯复合纸浸入摩尔浓度为0.05mol/L的抗坏血酸的乙醇溶液中进行化学还原，反应温度为30℃，反应时间为2小时，获得银掺杂石墨烯复合纸。通过上述方法可制备得到40μm厚的银掺杂石墨烯纸，水平方向热导率为570W/mK垂直热导率为3.2W/mK，方阻为70Ω/□。2 g of natural graphite and 4 g of sodium nitrate were uniformly mixed under ice water bath conditions, and then 182 ml of concentrated sulfuric acid was added, and stirred at 800 r/min for 15 min; 18 g of potassium permanganate was added, and the mixture was stirred at 800 r/min for 15 min to obtain a mixture. The mixture was transferred to a 40 ° C water bath, stirred for 15 min; 182 mL of deionized water was added, the reaction was carried out for 60 min, the water bath at 40 ° C was heated to 80 ° C, and the reaction was stirred for 300 min; 80 mL of a 30% by mass hydrogen peroxide solution was added. The reaction was continued for 90 min until the solution turned bright yellow. The reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide, and the rate of centrifugal cleaning was obtained. It is 5000r/min and the time is 30min. 2 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 4 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 4 g/L was obtained. 0.5 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 2 hours to obtain a mixed solution. The mixture was placed in a blast drying oven at 100 ° C for evaporation for 6 hours to obtain a silver-doped graphene oxide composite paper. Finally, the silver-doped graphene oxide composite paper was immersed in an ethanol solution of ascorbic acid having a molar concentration of 0.05 mol/L for chemical reduction, the reaction temperature was 30 ° C, and the reaction time was 2 hours to obtain a silver-doped graphene composite paper. A 40 μm thick silver-doped graphene paper can be prepared by the above method, and the horizontal thermal conductivity is 570 W/mK, the vertical thermal conductivity is 3.2 W/mK, and the square resistance is 70 Ω/□.
实施例4Example 4
在冰水浴条件下，将3g天然石墨与5g硝酸钠混合均匀，再加入230ml的浓硫酸，在300r/min条件下搅拌15min；加入30g高锰酸钾，在500r/min条件下搅拌100min得到混合液；将上述混合液移入35℃水浴中，反应150min；再加入460mL的去离子水，反应45min，将35℃的水浴升温至100℃，搅拌反应30min；加入200mL质量浓度为30％的双氧水，继续反应60min直到溶液变为亮黄色。将反应完全的混合溶液依次用质量浓度为30％的双氧水、质量浓度为10％的盐酸和蒸馏水进行离心清洗并干燥，获得氧化石墨烯，离心清洗的速率为1000r/min，时间为45min。称取氧化石墨烯粉末1g，加入0.5L去离子水，超声处理2h，功率为1000W，获得质量浓度为1g/L的氧化石墨烯悬浮液。向氧化石墨烯悬浮液中加入0.01g硝酸银，在300r/min条件下搅拌30min，得到混合液。再将混合液置于30℃的鼓风干燥箱中进行蒸发处理12小时，获得银掺杂氧化石墨烯复合纸。最后将银掺杂氧化石墨烯复合纸浸入摩尔浓度为5mol/L的硼氢化钠的甲醇溶液中进行化学还原，反应温度为100℃，反应时间为5小时，获得银掺杂石墨烯复合纸。通过上述方法可制备得到30μm厚的银掺杂石墨烯纸，水平方向热导率为602W/mK垂直热导率为3.3W/mK，方阻为65Ω/□。 In an ice water bath condition, 3 g of natural graphite and 5 g of sodium nitrate were uniformly mixed, 230 ml of concentrated sulfuric acid was added, and stirred at 300 r/min for 15 min; 30 g of potassium permanganate was added, and the mixture was stirred at 500 r/min for 100 min to obtain a mixture. The solution was transferred to a 35 ° C water bath for 150 min; 460 mL of deionized water was added, the reaction was carried out for 45 min, the water bath at 35 ° C was heated to 100 ° C, and the reaction was stirred for 30 min; 200 mL of a 30% by mass hydrogen peroxide solution was added. The reaction was continued for 60 min until the solution turned bright yellow. The reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide, and the rate of centrifugal cleaning was 1000 r/min for 45 minutes. 1 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 2 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 1 g/L was obtained. 0.01 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 30 minutes to obtain a mixed solution. The mixture was placed in a blast drying oven at 30 ° C for evaporation for 12 hours to obtain a silver-doped graphene oxide composite paper. Finally, the silver-doped graphene oxide composite paper was immersed in a methanol solution of sodium borohydride having a molar concentration of 5 mol/L for chemical reduction, the reaction temperature was 100 ° C, and the reaction time was 5 hours to obtain a silver-doped graphene composite paper. A 30 μm thick silver-doped graphene paper can be prepared by the above method, and the horizontal thermal conductivity is 602 W/mK, the vertical thermal conductivity is 3.3 W/mK, and the square resistance is 65 Ω/□.
实施例5Example 5
在冰水浴条件下，将2.5g天然石墨与5g硝酸钠混合均匀，再加入200ml的浓硫酸，在300r/min条件下搅拌15min；加入15g高锰酸钾，在500r/min条件下搅拌100min得到混合液；将上述混合液移入35℃水浴中，反应150min；再加入460mL的去离子水，反应45min，将35℃的水浴升温至100℃，搅拌反应30min；加入200mL质量浓度为30％的双氧水，继续反应60min直到溶液变为亮黄色。将反应完全的混合溶液依次用质量浓度为30％的双氧水、质量浓度为10％的盐酸和蒸馏水进行离心清洗并干燥，获得氧化石墨烯，离心清洗的速率为2000r/min，时间为30min。称取氧化石墨烯粉末1g，加入0.5L去离子水，超声处理2h，功率为1000W，获得质量浓度为1g/L的氧化石墨烯悬浮液。向氧化石墨烯悬浮液中加入0.01g硝酸银，在300r/min条件下搅拌30min，得到混合液。再将混合液置于30℃的鼓风干燥箱中进行蒸发处理12小时，获得银掺杂氧化石墨烯复合纸。最后将银掺杂氧化石墨烯复合纸浸入摩尔浓度为5mol/L的含有还原剂的溶液中进行化学还原，含有还原剂的溶液中，还原剂为质量比为1∶1的抗坏血酸和水合肼，溶剂为体积比为1∶1的四氢呋喃和二甲基甲酰胺。反应温度为40℃，反应时间为5小时，获得银掺杂石墨烯复合纸。通过上述方法可制备得到30μm厚的银掺杂石墨烯纸，水平方向热导率为479W/mK，垂直热导率为3.1W/mK，方阻为73Ω/□。Under ice water bath conditions, 2.5 g of natural graphite and 5 g of sodium nitrate were uniformly mixed, and then 200 ml of concentrated sulfuric acid was added, and stirred at 300 r/min for 15 min; 15 g of potassium permanganate was added, and stirred at 500 r/min for 100 min. Mixing solution; transferring the above mixture into a 35 ° C water bath for 150 min; adding 460 mL of deionized water for 45 min, heating the 35 ° C water bath to 100 ° C, stirring for 30 min; adding 200 mL of 30% hydrogen peroxide The reaction was continued for 60 min until the solution turned bright yellow. The reaction mixture was completely centrifuged and washed with hydrogen peroxide having a mass concentration of 30%, hydrochloric acid having a mass concentration of 10%, and distilled water to obtain graphene oxide. The rate of centrifugal cleaning was 2000 r/min, and the time was 30 min. 1 g of graphene oxide powder was weighed, 0.5 L of deionized water was added, sonicated for 2 h, and the power was 1000 W, and a graphene oxide suspension having a mass concentration of 1 g/L was obtained. 0.01 g of silver nitrate was added to the graphene oxide suspension, and the mixture was stirred at 300 r/min for 30 minutes to obtain a mixed solution. The mixture was placed in a blast drying oven at 30 ° C for evaporation for 12 hours to obtain a silver-doped graphene oxide composite paper. Finally, the silver-doped graphene oxide composite paper is immersed in a solution containing a reducing agent at a molar concentration of 5 mol/L for chemical reduction, and in the solution containing the reducing agent, the reducing agent is ascorbic acid and hydrazine hydrate in a mass ratio of 1:1. The solvent was tetrahydrofuran and dimethylformamide in a volume ratio of 1:1. The reaction temperature was 40 ° C and the reaction time was 5 hours to obtain a silver-doped graphene composite paper. A 30 μm thick silver-doped graphene paper was prepared by the above method, and the horizontal thermal conductivity was 479 W/mK, the vertical thermal conductivity was 3.1 W/mK, and the square resistance was 73 Ω/□.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (10)

  1. 一种银掺杂石墨烯复合纸的制备方法，包括如下步骤：A method for preparing a silver-doped graphene composite paper, comprising the following steps:
    制备氧化石墨烯，将所述氧化石墨烯进行超声处理，制备得到氧化石墨烯悬浮液；Preparing graphene oxide, sonicating the graphene oxide to prepare a graphene oxide suspension;
    向所述氧化石墨烯悬浮液中加入硝酸银得到混合液；Adding silver nitrate to the graphene oxide suspension to obtain a mixed liquid;
    将所述混合液进行蒸发处理，得到银掺杂氧化石墨烯复合纸；及The mixture is subjected to evaporation treatment to obtain a silver-doped graphene oxide composite paper;
    将所述银掺杂氧化石墨烯复合纸放入含有还原剂的溶液中进行还原处理，得到银掺杂石墨烯复合纸。The silver-doped graphene oxide composite paper is placed in a solution containing a reducing agent for reduction treatment to obtain a silver-doped graphene composite paper.
  2. 根据权利要求1所述的银掺杂石墨烯复合纸的制备方法，其特征在于，所述制备氧化石墨烯的方法具体为：The method for preparing a silver-doped graphene composite paper according to claim 1, wherein the method for preparing graphene oxide is specifically:
    在冰水浴条件下，将天然石墨和硝酸钠混合均匀，加入浓硫酸，搅拌10min～150min，然后加入高锰酸钾，继续搅拌10min～150min，得到混合液；Under the condition of ice water bath, the natural graphite and sodium nitrate are uniformly mixed, concentrated sulfuric acid is added, stirred for 10 min to 150 min, then potassium permanganate is added, and stirring is continued for 10 min to 150 min to obtain a mixed liquid;
    将所述混合液移入20℃～40℃恒温水浴中，搅拌反应15min～180min；向所述混合液中加入去离子水，反应30min～60min，然后将所述20℃～40℃恒温水浴的温度升至80℃～100℃，搅拌30min～300min；最后加入双氧水，反应30min～90min，洗涤、干燥得到氧化石墨烯。The mixed liquid is transferred into a constant temperature water bath of 20 ° C to 40 ° C, and the reaction is stirred for 15 min to 180 min; deionized water is added to the mixed solution, and the reaction is carried out for 30 min to 60 min, and then the temperature of the constant temperature water bath of 20 ° C to 40 ° C is taken. It is raised to 80 ° C ~ 100 ° C, stirred for 30 min ~ 300 min; finally added hydrogen peroxide, the reaction is 30 min ~ 90 min, washed and dried to obtain graphene oxide.
  3. 根据权利要求1所述的银掺杂石墨烯复合纸的制备方法，其特征在于，所述硝酸银与所述氧化石墨烯的质量比为0.01～1∶1～5。The method according to claim 1, wherein the mass ratio of the silver nitrate to the graphene oxide is 0.01 to 1:1 to 5.
  4. 根据权利要求1所述的银掺杂石墨烯复合纸的制备方法，其特征在于，所述将所述混合液进行蒸发处理的操作具体为：于30℃～150℃下蒸发0.5小时～24小时。The method for preparing a silver-doped graphene composite paper according to claim 1, wherein the operation of evaporating the mixed liquid is specifically: evaporating at 30 ° C to 150 ° C for 0.5 hours to 24 hours. .
  5. 根据权利要求4所述的银掺杂石墨烯复合纸的制备方法，其特征在于，所述将所述混合液进行蒸发处理的操作具体为：于60℃～100℃下蒸发6小时～12小时。The method for preparing a silver-doped graphene composite paper according to claim 4, wherein the operation of evaporating the mixed liquid is specifically: evaporating at 60 ° C to 100 ° C for 6 hours to 12 hours .
  6. 根据权利要求1所述的银掺杂石墨烯复合纸的制备方法，其特征在于，所述还原剂选自硼氢化钠、抗坏血酸及水合肼中的至少一种。The method for preparing a silver-doped graphene composite paper according to claim 1, wherein the reducing agent is at least one selected from the group consisting of sodium borohydride, ascorbic acid, and hydrazine hydrate.
  7. 根据权利要求1所述的银掺杂石墨烯复合纸的制备方法，其特征在于， 所述含有还原剂的溶液中，溶剂选自甲醇、乙醇、四氢呋喃及二甲基甲酰胺中的至少一种。The method for preparing a silver-doped graphene composite paper according to claim 1, wherein In the solution containing a reducing agent, the solvent is at least one selected from the group consisting of methanol, ethanol, tetrahydrofuran, and dimethylformamide.
  8. 根据权利要求1所述的银掺杂石墨烯复合纸的制备方法，其特征在于，所述含有还原剂的溶液的浓度为0.01mol/L～5mol/L。The method according to claim 1, wherein the concentration of the solution containing the reducing agent is from 0.01 mol/L to 5 mol/L.
  9. 根据权利要求1所述的银掺杂石墨烯复合纸的制备方法，其特征在于，所述将所述银掺杂氧化石墨烯复合纸放入含有还原剂的溶液中进行还原处理的步骤具体为：将所述含有还原剂的溶液加热至30℃～150℃，将所述银掺杂氧化石墨烯复合纸放入温度为30℃～150℃的含有还原剂的溶液中反应0.5小时～10小时。The method for preparing a silver-doped graphene composite paper according to claim 1, wherein the step of placing the silver-doped graphene oxide composite paper in a solution containing a reducing agent for reduction treatment is specifically : heating the solution containing the reducing agent to 30 ° C to 150 ° C, and placing the silver-doped graphene oxide composite paper in a solution containing a reducing agent at a temperature of 30 ° C to 150 ° C for 0.5 hour to 10 hours. .
  10. 一种由权利要求1～9任一项所述的银掺杂石墨烯复合纸的制备方法制备的银掺杂石墨烯复合纸。 A silver-doped graphene composite paper prepared by the method for preparing a silver-doped graphene composite paper according to any one of claims 1 to 9.
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