CN102436862A - Graphene/nanometer copper electric conducting composite material and preparation thereof - Google Patents
Graphene/nanometer copper electric conducting composite material and preparation thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene/nanometer copper composite material, and belongs to the technical field of composite materials. The preparation method is characterized by comprising the following steps: carrying out disgregation on graphene by taking N-methyl pyrrolidone as a solvent; dropping a copper sulphate solution gradually in the N-methyl pyrrolidone simultaneously; and then carrying out synchronous restoration and oxidation on graphene and bluestone by a one-step method by utilizing vitamin C as a reducer again so as to prepare the graphene/nanometer copper composite material. In the invention, copper nanometer particles are uniformly dispersed on the surface of graphene in the prepared composite material, the prepared composite material has good electric performance and better heat stability, the processability of graphene is greatly improved, thereby being used for fields such as a high temperature electricity conducting material, a processing high current-conducting nanometer device and conductive adhesive and the like. The preparation method provided by the invention has the advantages of simple technology, convenience in operation, genial reaction condition, no pollution, low manufacturing cost, high production efficiency, and has good industrialized production prospect.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of preparation method of Graphene/metal nanoparticle, the preparation method of particularly a kind of Graphene/nanometer carbon/carbon-copper composite material.
Background technology
Since 2004, since Graphene comes to light, caused global research boom, so far, found that Graphene all has many peculiar character at aspects such as light, electricity, magnetic.It is the thinnest at present known, the hardest, the best a kind of material of electric conductivity, can be used for preparing electrode, composite material, battery, super capacitor, hydrogen storage material, field emmision material and the hypersensitive sensing material etc. of organic electro-optic device.Graphene has outstanding electric property.At present, people have produced keen interest to the research of graphene-based metal inorganic nano composition, in the hope of preparing a kind of functional material with excellent specific property.
The good characteristic of nano copper particle is able to promote the well-being of mankind.The specific area of copper nanoparticle is big, surface activity center number is many, in metallurgical and petrochemical industry, is good catalyst.The nanoscale copper powder is the same with its block materials to have very high thermal conductivity and conductivity, can be used for making electrocondution slurry (conducting resinl, magnetic-conductive adhesive etc.), and is used for encapsulation, the connection of microelectronics industry, and the miniaturization of microelectronic component is played an important role.From middle nineteen nineties in last century; After the Pokka of IBM etc. points out that nanometer copper can be used to the electronics connection owing to its low resistance; Its special electrical properties causes the very big concern of electronics circle, and increasing researcher begins diversion on the preparation and application of nanometer copper.In the application of structural timber, nanometer copper crystal material has good tensile property and impact strength, and its mechanical property is compared the lifting that has clearly with traditional copper material.In addition, copper nanoparticle is high conductivity, the indispensable basic material of high-intensity nanometer copper material, so the development of copper nanoparticle and the composite material relevant with it has important significance for theories and practical value.
Summary of the invention
The objective of the invention is to utilize the electric property of Graphene, the high conductivity of metal nanoparticle, high rigidity and thermal stability provide a kind of Graphene/nanometer carbon/carbon-copper composite material with superior electrical performance, mechanical performance and thermal stability.
The preparation method of a kind of Graphene/nanometer carbon/carbon-copper composite material is characterized in that: graphite oxide is scattered in the N-methyl pyrrolidone ultrasonic, obtains finely dispersed graphite oxide suspension; Regulator solution pH=9-10, adding mass concentration is the copper-bath of 1.57g/L ~ 7.67g/L, under agitation, adds vitamin C as reducing agent, at 85 ℃ ~ 95 ℃ back flow reaction 1.5h ~ 3.0h; Product is filtered, and after the distilled water washes clean, drying is ground, and obtains Graphene/nanometer Cu composite material.
The mass ratio of said graphite oxide and copper sulphate is 1:0.8 ~ 1:3.
The ascorbic addition of said reducing agent is 2.45 ~ 6.67 times of graphite oxide quality.
Through infrared spectrogram, TEM|, SEM photo and TG curve and conductivity the structure and the performance of the Graphene/nanometer Cu composite material of the present invention's preparation are tested and characterized below.
1. infrared spectrum analysis
Fig. 1 is the FTIR spectrogram of graphite oxide; Fig. 2 is Graphene (b), and the FTIR spectrogram of Graphene/nanometer Cu composite material (c).In the spectrogram of Fig. 1 graphite oxide, 3440cm
-1Be the stretching vibration peak of-OH, 1728 cm
-1Be the stretching vibration peak of C=O in the carboxyl, 1404 cm
-1Be the in-plane bending vibration peak of-OH, 1055 cm
-1Stretching vibration peak for C-O.The spectrogram of Fig. 2 Graphene is very similar with the spectrogram of Fig. 1 graphite oxide, after this explanation Graphene is reduced, recovered its conjugated structure basically, but curve is few than the smooth functional group of graphite oxide, is reduced basically.The spectrogram of Fig. 2 Graphene/nanometer Cu composite material (c) is compared with the spectrogram of Graphene (b), has had more the several characteristic absworption peak, and this explanation recombination process has the combination of chemical bond between them, has generated new functional group.This phenomenon shows, in the middle of the forming process of composite material, the chemical bonding effect has taken place between Cu and the Graphene, rather than the absorption of physics.
2. electronic microscope photos
Fig. 3 is the transmission electron microscope photo of Graphene.As can beappreciated from fig. 3, luminous energy partly sees through its lamella, and its pattern is as the silk of accordion, and this is the characteristic that the material of sheet layer can not possess, and explains that the Graphene of this method preparation is very thin on thickness direction.It is deep mixed also to can be observed Graphene lamella each several part field color simultaneously, and light transmission is not quite similar, and lamella upper end color is obviously shallow than the lower end, and the Graphene that this explanation makes is not the monolithic layer structure entirely, but is formed by stacking several monolithic layer.Fig. 4 is the stereoscan photograph of Graphene/Cu composite material.Can see clearly that from Fig. 4 tablet is the graphene platelet of piling up each other, the Cu nano particle is coated on the surface of Graphene even, densely.According to the engineer's scale among Fig. 4; The thickness that we can draw Graphene is 1nm; To compare numerical value bigger than normal with the thickness (0.34nm) of single-layer graphene for this; The reason that causes this phenomenon possibly be that the Graphene surface has coated the Cu nano particle, also might be that three layer graphenes are deposited in thickness together.The particle diameter of nano Cu particle is 10nm, is coated on the surface of Graphene uniformly, and Graphene lamella edge coat more, explain in the edge of Graphene stronger to the absorption affinity of Cu particle.
3. thermogravimetric analysis
Fig. 5 is the TG curve of graphite oxide, Graphene, Graphene/nanometer Cu composite material.Among the figure, (1) is the TG curve of graphite oxide.Can find out that from Fig. 5 (1) the thermal weight loss process of graphite oxide can be divided into 3 stages: the phase I is the starting stage of heating up, and temperature is 20 ~ 190 ℃.In this stage, along with temperature raises, the graphite oxide surface moisture evaporates, and causes the weightlessness of graphite oxide, and the weight-loss ratio of this moment is main relevant with the degree of drying of material.Second stage is the sharply weightless stage of graphite oxide, and temperature is 200 ~ 500 ℃.Functional group on this stage graphite oxide surface begins to decompose, and it is the Main Stage of pyrolysis.Phase III is the process that the graphite oxide carbon skeleton decomposes gradually, and temperature is 500 ~ 600 ℃.(2) are the TG curve of Graphene among the figure.From figure (2), can find out that Graphene thermal weight loss process can be divided into 3 stages: the phase I is the starting stage of heating up, and temperature is 20 ~ 100 ℃.In this stage, along with temperature raises, the evaporation of Graphene surface moisture causes that Graphene is weightless.Second stage is the stage of the slow weightlessness of Graphene, and temperature is 100 ℃ ~ 400 ℃.This stage is weightless and not obvious, causes that weightless reason possibly be that Graphene some impurity in the preparation process decompose caused.Phase III weightlessness is apparent in view, and temperature is 400 ~ 700 ℃.The weightlessness in this stage mainly is owing to some organo-functional groups that remain in the Graphene surface take place to decompose caused.(3) are the TG curve of Graphene/nanometer Cu composite material among the figure.As can be seen from the figure; Composite material weightlessness in the middle of whole process is not too obvious, and slight weightlessness takes place compound before 400 ℃ from beginning to warm to, and mainly is that dehydration is caused in evaporation of water and the complex molecule; At 400 ℃ ~ 800 ℃; Apparent in view weightlessness occurs, this and pure Graphene weight-loss curve are similar, are that the Graphene surface functional group decomposes and causes in the compound; After 800 ℃, the decomposition of the carbon skeleton of Graphene has caused certain weightlessness, and it is stable that remaining mass keeps, residue 73%.Thereby can know; Graphene is stable higher than graphite oxide; Graphene/Cu composite material is stable higher than Graphene; Reason possibly be nanometer copper Cu on the surface of Graphene, himself have excellent thermal stability, and further stoped the decomposition of the more lip-deep residual organo-functional groups of Graphene.
4. electric conductivity analysis:
Table 1 is the conductivity of composite material, and 1 can find out from table, and the conductive capability of composite material is along with adding CuSO
4Concentration increase and increase, at CuSO
4Concentration be 4.68g/L; Its conductivity reaches maximum 0.74 S/cm, and then conductivity begins to drop to 0.65 S/cm, and this mainly is owing to the increase along with nano Cu particle; Between the thin slice of Graphene, formed conductive path, thereby conductance increases constantly through bridged linkage; To CuSO
4Mass concentration be that 4.68g/L reaches maximum, afterwards along with the increase of Cu quality, influenced the original conduction system of Graphene, composite material shows the similar character with Cu, thereby conductivity begins to descend.Table 1 is for adding CuSO
4The relation of conductivity of mass concentration and composite material.
Table 1
CuSO 4Mass concentration (g/L) | 1.57 | 3.10 | 4.68 | 6.16 | 7.67 |
Conductivity (S/cm) | 0.48 | 0.57 | 0.74 | 0.68 | 0.65 |
In sum; Graphene/nanometer Cu the composite material of the present invention's preparation, nano Cu particle is coated on the surface of graphene platelet equably, makes it have good electric conductivity and thermal stability; Therefore can be used for the high-temperature electric conduction material, fields such as the nano-device of the high conduction of processing and conducting resinl.
In addition, technology of the present invention is simple, and is easy to operate, and reaction condition is gentle, and pollution-free, production cost is low, and production efficiency is high, has the favorable industrial prospect of production.
Description of drawings
Fig. 1 is the infrared spectrogram of graphite oxide.
Fig. 2 is the infrared spectrogram of Graphene (b) and Graphene/nanometer Cu (c).
Fig. 3 is the transmission electron microscope photo of Graphene.
Fig. 4 is the stereoscan photograph of Graphene/nanometer Cu composite material when amplifying 70,000 times.
Fig. 5 is the thermogravimetric analysis figure of graphite oxide (1), Graphene (2), Graphene/nanometer Cu composite material (3).
Embodiment
Embodiment 1
1. the preparation of graphite oxide: 1g 200 order natural graphite powders are under agitation slowly joined in the beaker of the 500ml that the 23ml concentrated sulfuric acid is housed, and temperature maintenance slowly adds the mixture of 0.5g sodium nitrate and 3g potassium permanganate again at 0 ℃; At 0 ℃ of following stirring reaction 2h; Again in 35 ℃ the water bath with thermostatic control, stir insulation 30min down afterwards, slowly add 46ml water; Make temperature rise to 98 ℃, under this temperature, keep 15min; Be diluted to 140ml with warm water, pour certain amount of H into
2O
2, at this moment solution colour becomes glassy yellow, filters while hot, with the abundant washing leaching cake of 5% HCl, in filtrating, does not have SO
4 2-(use BaCl
2Solution detects), anhydrous CaCl under 50 ℃
2In vacuumize 24h, obtain the graphite oxide powder under existing.
2. the preparation of Graphene/nanometer Cu composite material: the adding of 0.3g graphite oxide is equipped with in the 250ml three-necked bottle of 150ml N-methyl pyrrolidone; Ultrasonic dispersion 1h; Regulate its pH to 9 with NaOH solution, under agitation add the 2g vitamin C, dropwise splash into the CuSO of 46ml 0.1mol/L while stirring
4Solution, 90 ℃ of refluxed 2h filter product, use the distilled water washes clean repeatedly after, under 50 ℃ in baking oven dry 24h, obtain Graphene/nanometer Cu composite material.
The conductivity of the Graphene/nanometer Cu composite material of present embodiment preparation is 0.65S/cm.
Embodiment 2
1. the method for making of graphite oxide is identical with embodiment 1
2. the preparation of Graphene/nanometer Cu composite material: the adding of 0.3g graphite oxide is equipped with in the 250ml three-necked bottle of 150ml N-methyl pyrrolidone; Ultrasonic dispersion 1h; Regulate its pH to 9.5 with NaOH solution; Under agitation add the 1.71g vitamin C, dropwise splash into the CuSO of 37.5ml 0.1mol/L while stirring
4Solution, 90 ℃ of refluxed 2h filter product, use the distilled water washes clean repeatedly after, under 50 ℃ in baking oven dry 24h, obtain Graphene/nanometer Cu composite material.
The conductivity of the Graphene/nanometer Cu composite material of present embodiment preparation is 0.68S/cm.
Embodiment 3
1. the method for making of graphite oxide is identical with embodiment 1
2. the preparation of Graphene/nanometer Cu composite material: the adding of 0.3g graphite oxide is equipped with in the 250ml three-necked bottle of 150ml N-methyl pyrrolidone; Ultrasonic dispersion 1h; Regulate its pH to 10 with NaOH solution; Under agitation add the 1.38g vitamin C, dropwise splash into the CuSO of 28.1ml 0.1mol/L while stirring
4Solution, 90 ℃ of refluxed 2h filter product, use the distilled water washes clean repeatedly after, under 50 ℃ in baking oven dry 24h, obtain Graphene/nanometer Cu composite material.
The conductivity of the Graphene/nanometer Cu composite material of present embodiment preparation is 0.74S/cm.
Embodiment 4
1. the method for making of graphite oxide is identical with embodiment 1
2. the preparation of Graphene/nanometer Cu composite material: the adding of 0.3g graphite oxide is equipped with in the 250ml three-necked bottle of 150ml N-methyl pyrrolidone; Ultrasonic dispersion 1h; Regulate its pH to 9 with NaOH solution; Under agitation add the 1.06g vitamin C, dropwise splash into the CuSO of 18.6ml 0.1mol/L while stirring
4Solution, 90 ℃ of refluxed 2h filter product, use the distilled water washes clean repeatedly after, under 50 ℃ in baking oven dry 24h, obtain Graphene/nanometer Cu composite material.
The conductivity of the Graphene/nanometer Cu composite material of present embodiment preparation is 0.57S/cm.
Embodiment 5
1. the method for making of graphite oxide is identical with embodiment 1
2. the preparation of Graphene/Cu composite material: the adding of 0.3g graphite oxide is equipped with in the 250ml three-necked bottle of 150ml N-methyl pyrrolidone; Ultrasonic dispersion 1h; Regulate its pH to 9.5 with NaOH solution; Under agitation add the 0.74g vitamin C, dropwise splash into the CuSO of 9.4ml 0.1mol/L while stirring
4Solution, 90 ℃ of refluxed 2h filter product, use the distilled water washes clean repeatedly after, under 50 ℃ in baking oven dry 24h, obtain Graphene/nanometer Cu composite material.
The conductivity of the Graphene/nanometer Cu composite material of present embodiment preparation is 0.48S/cm.
Claims (5)
1. the preparation method of Graphene/nanometer carbon/carbon-copper composite material is characterized in that: graphite oxide is scattered in the N-methyl pyrrolidone ultrasonic, obtains finely dispersed graphite oxide suspension; Regulator solution pH=9-10, adding concentration is the copper-bath of 1.57g/L ~ 7.67g/L, under agitation, adds vitamin C as reducing agent, at 85 ℃ ~ 95 ℃ back flow reaction 1.5h ~ 3.0h; Product is filtered, and after the distilled water washes clean, drying is ground, and obtains Graphene/nanometer carbon/carbon-copper composite material.
2. the preparation method of Graphene/nanometer carbon/carbon-copper composite material according to claim 1, it is characterized in that: the mass ratio of said graphite oxide and copper sulphate is 1:0.8 ~ 1:3.
3. the preparation method of Graphene/nanometer carbon/carbon-copper composite material according to claim 1, it is characterized in that: the ascorbic addition of said reducing agent is 2.45 ~ 6.67 times of graphite oxide quality.
4. Graphene/nanometer the carbon/carbon-copper composite material of method preparation according to claim 1.
5. like the said Graphene of claim 4/nanometer carbon/carbon-copper composite material, it is characterized in that: nanometer copper particle is coated on the surface of Graphene uniformly.
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