CN113430408A - High-conductivity nickel-modified graphene/copper composite material and preparation method thereof - Google Patents
High-conductivity nickel-modified graphene/copper composite material and preparation method thereof Download PDFInfo
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Abstract
A high-conductivity nickel-modified graphene/copper composite material and a preparation method thereof are disclosed, wherein a two-step hydrothermal method is firstly used for loading nickel on graphene to prepare Ni-Gr powder, the Ni-Gr powder is mixed with copper powder and subjected to ball milling to obtain mixed powder, and the mixed powder is sintered to obtain the nickel-modified graphene/copper composite material; the preparation method is simple to operate, free of pollution and low in cost; the thermal conductivity of the obtained composite material is superior to that of pure copper, particularly the high-temperature thermal conductivity of the composite material is good, and the electrical conductivity of the nickel modified graphene in the composite material within a certain range is higher than that of the pure copper.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a high-conductivity nickel-modified graphene/copper composite material and a preparation method thereof.
Background
In the field of electric conduction, copper and copper-based composite materials have extremely wide application and research. Copper has good conductivity, is second to silver, is cheap and has good economy; the carrier mobility of graphene is 15000cm2Has a thermal conductivity of 5300W/m.K (single layer)So as to effectively conduct electricity and heat conduction; how to enhance the wettability of copper and graphene is the problem to be solved.
The publication number is CN104030277A, the name of the invention is that in the prior art 1 of preparing graphene by a chemical vapor deposition method, copper and graphene are compounded by the chemical vapor deposition method; the publication number is CN110788344A, the invention is named as prior art 2 of a preparation method of loading metal nanoparticles with different contents on the surface of graphene, metal salt solution is mixed with glucose and NaCl solution, and nickel modified graphene nanosheets are prepared by chemical vapor deposition; however, both the prior art 1 and the prior art 2 have the technical problems of complex preparation process and high preparation cost.
Therefore, in order to further improve the electric conductivity and the heat conductivity of the copper conductive material and the potential of industrial production, a graphene reinforced copper-based composite electrode material which has excellent performance and low cost and can be produced in a large scale needs to be designed and synthesized.
Disclosure of Invention
The invention aims to provide a preparation method of a high-conductivity nickel-modified graphene/copper composite material, and aims to solve the technical problems of complex preparation process and long preparation time in the prior art.
In order to solve the technical problem, the preparation method of the high-conductivity nickel-modified graphene/copper composite material comprises the following steps:
loading nickel on graphene by using a two-step hydrothermal method to prepare Ni-Gr powder;
mixing the Ni-Gr powder prepared in the step I with copper powder and performing ball milling to obtain mixed powder;
and step three, sintering the mixed powder prepared in the step two to obtain the nickel modified graphene/copper composite material.
Preferably, the step (i) specifically includes the steps of:
a, preparing graphene dispersion liquid, adding nickel acetate and urea solution into the graphene dispersion liquid, and stirring to prepare solution A;
b, preserving the heat of the solution A prepared in the step a at high temperature, and extracting a precipitate, namely the precipitate A;
and c, dispersing the precipitate A obtained in the step B in deionized water, dropwise adding a potassium borohydride solution, heating at constant temperature by a hydrothermal method, taking the precipitate, marking as a precipitate B, drying the precipitate B, and grinding to obtain Ni-Gr powder.
The preparation method of the high-conductivity nickel-modified graphene/copper composite material has the following advantages:
firstly, metal nano particles are innovatively loaded on graphene to be used for modifying the graphene, so that the binding property of the graphene and copper is enhanced, and the wetting capacity of the copper and the graphene is improved;
secondly, the operation is simple, the reaction temperature is low, the cost is low, no pollution is caused, and the repeatability is good;
thirdly, in order to overcome the technical defects of high production cost and low efficiency of the nickel modified graphene prepared by using a chemical vapor deposition method in the prior art, the invention provides a simple method for synthesizing the nickel modified graphene by using a two-step hydrothermal method to improve the wetting capacity of copper and graphene, and the first step of hydrothermal production is Ni (OH)2The second step is mixing Ni (OH)2The nickel nanoparticles are reduced to form nickel nanoparticles, so that the binding property of the nickel nanoparticles and graphene is improved;
selecting nickel acetate as a nickel salt and urea as a precipitator, and reducing pure nickel nanoparticles without other impurities under the condition of keeping the original structure of the graphene;
and the dosage of the graphene is less, so that the cost of the composite material can be reduced.
The invention also aims to provide a high-conductivity nickel-modified graphene/copper composite material, which is prepared by the preparation method of the high-conductivity nickel-modified graphene/copper composite material.
The high-conductivity nickel-modified graphene/copper composite material has the following advantages:
the thermal conductivity of the composite material is superior to that of pure copper, when the addition amount of the nickel modified graphene is 0.1 wt%, the thermal conductivity change curve of the nickel modified graphene is consistent with that of the pure copper when the temperature rises, and when the addition amount of the nickel modified graphene is 0.2-0.3 wt%, the thermal conductivity of the nickel modified graphene rises along with the temperature rise, so that the addition of the nickel modified graphene is more beneficial to improving the high-temperature thermal conductivity of the composite material;
when the addition amount of the nickel modified graphene is less than 0.2 wt%, the conductivity of the nickel modified graphene is higher than that of pure copper, and when the addition amount of the nickel modified graphene is continuously increased, the conductivity of the nickel modified graphene is lower than that of the pure copper, which indicates that the excessive graphene promotes the electron scattering capability of a sample, hinders the transmission of electrons, and causes the conductivity to be reduced;
the structure is that multilayer graphene is attached to copper powder, graphene is embedded into a substrate in a lamellar mode, nano nickel particles are uniformly loaded on the corrugated graphene, nickel plays a role in cross bonding from the middle, wettability of the graphene and copper is improved, and a graphene-nickel particle-copper combination state is formed.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample e prepared by comparative example 1 of the present invention;
FIG. 2 is a Scanning Electron Micrograph (SEM) of pure copper powder;
FIG. 3 is a Scanning Electron Micrograph (SEM) of sample e prepared according to comparative example 1 of the present invention;
FIG. 4 is a Scanning Electron Micrograph (SEM) of sample b prepared according to example 2 of the present invention;
FIG. 5 is a Scanning Electron Micrograph (SEM) of sample b prepared according to example 2 of the present invention after etching;
FIG. 6 is a graph comparing the electrical conductivity at 25 ℃ for samples a, b, c, d prepared in examples 1-4 of the present invention;
FIG. 7 is a graph comparing the thermal conductivity curves at 25 deg.C to 300 deg.C for samples a, b, c, and d prepared in examples 1-4 of the present invention;
FIG. 8 is a graph comparing thermal conductivities at 25 ℃ and 300 ℃ for samples a, b, c, d prepared according to examples 1-4 of the present invention.
Detailed Description
In order to better understand the purpose, structure and function of the present invention, the following describes in detail a method for preparing a highly conductive nickel-modified graphene/copper composite material according to the present invention with reference to the accompanying drawings.
Example 1
A preparation method of a high-conductivity nickel modified graphene/copper composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 6 hours at 160 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
step 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 1mol/L potassium borohydride solution into the deionized water, stirring for 10min, performing hydrothermal treatment at 180 ℃ for 8h, performing centrifugal washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 24h, and grinding to obtain Ni-Gr powder;
and 5, mixing the Ni-Gr powder prepared in the step 4 with 10g of copper powder to obtain composite powder with the mass of the Ni-Gr powder being 0.05 wt%, wherein the ball-to-material ratio is 20: 1, ball-milling the composite powder for 5 hours at the rotation speed of 500rpm, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain mixed powder;
step 6, sintering the nickel-modified graphene/copper composite material prepared in the step 5 in a discharge plasma sintering furnace at the sintering pressure of 40MPa and the sintering temperature of 800 ℃ for 5min, and cooling along with the furnace to obtain a blank of the nickel-modified graphene/copper composite material;
and 7, polishing the blank of the nickel-modified graphene/copper composite material prepared in the step 6 to obtain the nickel-modified graphene/copper composite material, and marking as a sample a.
In the first hydrothermal process of this example, urea was used to provide an alkaline environment and was reacted with nickel acetate to form Ni (OH)2The inventor adopts nickel sulfate and sodium hydroxide in the research and development process, but easily introduces impurity sodium ions and sulfur ions because of selecting urea and nickel acetate and not introducing other impurity ionsOther nickel salts and precipitants not employed but not introduced with impurity ions are also contemplated as falling within the scope of the present invention.
The second hydrothermal method using potassium borohydride as strong reducing agent, adding Ni (OH)2The reduction is carried out to Ni, and potassium borohydride can be replaced by strong reducing agents such as sodium borohydride and the like.
The sintering mode of the copper and nickel modified graphene adopts a spark plasma sintering mode, so that the temperature rise rate is high, the sample is uniformly heated, the heat preservation time is short, the crystal grains are prevented from growing, and the defects are reduced.
Example 2
A preparation method of a high-conductivity nickel modified graphene/copper composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 6 hours at 160 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
step 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 1mol/L potassium borohydride solution into the deionized water, stirring for 10min, performing hydrothermal treatment at 180 ℃ for 8h, performing centrifugal washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 24h, and grinding to obtain Ni-Gr powder;
and 5, mixing the Ni-Gr powder prepared in the step 4 with 10g of copper powder to obtain composite powder with the mass ratio of the Ni-Gr powder being 0.1 wt%, wherein the ball-to-material ratio is 20: 1, ball-milling the composite powder for 5 hours at the rotation speed of 500rpm, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain mixed powder;
step 6, sintering the nickel-modified graphene/copper composite material prepared in the step 5 in a discharge plasma sintering furnace at the sintering pressure of 40MPa and the sintering temperature of 800 ℃ for 5min, and cooling along with the furnace to obtain a blank of the nickel-modified graphene/copper composite material;
and 7, polishing the blank of the nickel-modified graphene/copper composite material prepared in the step 6 to obtain the nickel-modified graphene/copper composite material, and marking as a sample b.
Example 3
A preparation method of a high-conductivity nickel modified graphene/copper composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 6 hours at 160 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
step 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 1mol/L potassium borohydride solution into the deionized water, stirring for 10min, performing hydrothermal treatment at 180 ℃ for 8h, performing centrifugal washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 24h, and grinding to obtain Ni-Gr powder;
and 5, mixing the Ni-Gr powder prepared in the step 4 with 10g of copper powder to obtain composite powder with the mass ratio of the Ni-Gr powder being 0.2 wt%, wherein the ball-to-material ratio is 20: 1, ball-milling the composite powder for 5 hours at the rotation speed of 500rpm, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain mixed powder;
step 6, sintering the nickel-modified graphene/copper composite material prepared in the step 5 in a discharge plasma sintering furnace at the sintering pressure of 40MPa and the sintering temperature of 800 ℃ for 5min, and cooling along with the furnace to obtain a blank of the nickel-modified graphene/copper composite material;
and 7, polishing the blank of the nickel-modified graphene/copper composite material prepared in the step 6 to obtain the nickel-modified graphene/copper composite material, and marking as a sample c.
Example 4
A preparation method of a high-conductivity nickel modified graphene/copper composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 6 hours at 160 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
step 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 1mol/L potassium borohydride solution into the deionized water, stirring for 10min, performing hydrothermal treatment at 180 ℃ for 8h, performing centrifugal washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 24h, and grinding to obtain Ni-Gr powder;
and 5, mixing the Ni-Gr powder prepared in the step 4 with 10g of copper powder to obtain composite powder with the mass ratio of the Ni-Gr powder being 0.3 wt%, wherein the ball-to-material ratio is 20: 1, ball-milling the composite powder for 5 hours at the rotation speed of 500rpm, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain mixed powder;
step 6, sintering the nickel-modified graphene/copper composite material prepared in the step 5 in a discharge plasma sintering furnace at the sintering pressure of 40MPa and the sintering temperature of 800 ℃ for 5min, and cooling along with the furnace to obtain a blank of the nickel-modified graphene/copper composite material;
and 7, grinding and polishing the blank of the nickel-modified graphene/copper composite material prepared in the step 6 to obtain the nickel-modified graphene/copper composite material, and marking as a sample d.
Example 5
A preparation method of a high-conductivity nickel modified graphene/copper composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 6 hours at 180 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
step 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 1mol/L potassium borohydride solution into the deionized water, stirring for 10min, performing hydrothermal treatment at 160 ℃ for 8h, performing centrifugal washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 24h, and grinding to obtain Ni-Gr powder;
and 5, mixing the Ni-Gr powder prepared in the step 4 with 10g of copper powder to obtain composite powder with the mass ratio of the Ni-Gr powder being 0.3 wt%, wherein the ball-to-material ratio is 20: 1, ball-milling the composite powder for 5 hours at the rotation speed of 500rpm, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain mixed powder;
step 6, sintering the nickel-modified graphene/copper composite material prepared in the step 5 in a discharge plasma sintering furnace at the sintering pressure of 40MPa and the sintering temperature of 800 ℃ for 5min, and cooling along with the furnace to obtain a blank of the nickel-modified graphene/copper composite material;
and 7, polishing the blank of the nickel-modified graphene/copper composite material prepared in the step 6 to obtain the nickel-modified graphene/copper composite material.
Example 6
A preparation method of a high-conductivity nickel modified graphene/copper composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving the graphite in deionized water, and obtaining the graphite in the step 1Mixing the alkene dispersion liquid with the alkene dispersion liquid, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 8 hours at 140 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
step 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 0.5mol/L potassium borohydride solution into the deionized water, stirring for 10min, performing hydrothermal treatment at 160 ℃ for 8h, performing centrifugal washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 24h, and grinding to obtain Ni-Gr powder;
and 5, mixing the Ni-Gr powder prepared in the step 4 with 10g of copper powder to obtain composite powder with the mass ratio of the Ni-Gr powder being 0.1 wt%, wherein the ball-to-material ratio is 20: 1, ball-milling the composite powder for 5 hours at the rotation speed of 500rpm, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain mixed powder;
step 6, sintering the nickel-modified graphene/copper composite material prepared in the step 5 in a discharge plasma sintering furnace at the sintering pressure of 40MPa and the sintering temperature of 800 ℃ for 5min, and cooling along with the furnace to obtain a blank of the nickel-modified graphene/copper composite material;
and 7, polishing the blank of the nickel-modified graphene/copper composite material prepared in the step 6 to obtain the nickel-modified graphene/copper composite material.
Example 7
A preparation method of a high-conductivity nickel modified graphene/copper composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 8 hours at 140 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
step 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 0.5mol/L potassium borohydride solution into the deionized water, stirring for 10min, heating for 10h at 160 ℃, centrifugally washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 12h, and grinding to obtain Ni-Gr powder;
and 5, mixing the Ni-Gr powder prepared in the step 4 with 10g of copper powder to obtain composite powder with the mass ratio of the Ni-Gr powder being 0.05 wt%, wherein the ball-to-material ratio is 20: 1, ball-milling the composite powder for 5 hours at the rotation speed of 500rpm, and then carrying out vacuum drying for 6 hours at 80 ℃ to obtain mixed powder;
step 6, sintering the nickel-modified graphene/copper composite material prepared in the step 5 in a discharge plasma sintering furnace at the sintering pressure of 40MPa and the sintering temperature of 800 ℃ for 5min, and cooling along with the furnace to obtain a blank of the nickel-modified graphene/copper composite material;
and 7, polishing the blank of the nickel-modified graphene/copper composite material prepared in the step 6 to obtain the nickel-modified graphene/copper composite material.
Comparative example 1
A preparation method of a high-conductivity nickel modified graphene composite material comprises the following steps:
step 2, weighing 1mmol (CH)3COO)2Ni、0.5mmol CON2H4Dissolving in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 10min to obtain a solution A;
step 3, putting the solution A obtained in the step 2 into a polytetrafluoroethylene reaction kettle, heating for 6 hours at 160 ℃, centrifuging and washing until the supernatant is transparent, and taking the precipitate as precipitate A;
and 4, dispersing the precipitate A prepared in the step 3 into deionized water, dropwise adding 0.5mol/L potassium borohydride solution into the deionized water, stirring for 10min, performing hydrothermal treatment at 180 ℃ for 8h, performing centrifugal washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 60 ℃ for 12h, and grinding to obtain Ni-Gr powder, marking as sample e.
Electrochemical performance analysis was performed on sample a prepared in example 1, sample b prepared in example 2, sample c prepared in example 3, and sample d prepared in example 4 as follows:
first, X-ray diffraction analysis
FIG. 1 is an X-ray diffraction pattern of a sample e prepared in comparative example 1, in which the X-ray diffraction curve of the sample e is compared with Ni standard cards (vertical lines on the abscissa), and it can be seen that peaks of the X-ray diffraction curve correspond to the Ni standard cards one-to-one, and the sample e is successfully loaded with nickel.
Second, comparative analysis of Scanning Electron Microscopy (SEM)
FIG. 2 is a topographical view of pure copper powder; fig. 3 is nickel-modified graphene powder prepared by a two-step hydrothermal method, and it can be seen from the figure that nano nickel particles are more uniformly loaded on the corrugated graphene; fig. 4 is a composite powder of copper powder and nickel modified graphene ball-milled for 5h, in which it can be seen that multiple layers of graphene are attached to the copper powder, and nickel is used as a coupling agent from the middle to form a graphene-nickel particle-copper bonding state; fig. 5 is a morphology diagram of the composite material after corrosion, and it can be seen from the diagram that the number of graphene layers is small, no significant aggregation is generated, the addition amount of graphene is small, and only a small amount of graphene is embedded into the matrix in a lamellar manner.
Third, comparative analysis of conductivity
Fig. 6 shows the conductivity change of the composite material with the graphene addition amounts of 0, 0.05, 0.1, 0.2, and 0.3 wt%, i.e., the conductivity of the sample a, the sample b, the sample c, and the sample d at 25 ℃ and room temperature, and it can be seen from the graph that the conductivity is in the trend of rising first and falling second, which indicates that the addition of a proper amount of graphene is helpful to improve the conductivity of the composite material, and when the addition amount of the Ni-modified graphene is 0.1 wt%, the conductivity reaches 95.78%, while the conductivity of the pure copper sample prepared by the same process method is 90.74%, and the conductivity of the sample b is improved by 5.04% compared with the conductivity of the pure copper sample. The conductivity of the sample c is similar to that of pure copper, and the conductivity of the sample d is obviously reduced, which indicates that the excessive graphene promotes the electron scattering capability of the sample, hinders the transmission of electrons and causes the reduction of the conductivity.
Fourth, comparative analysis of thermal conductivity
As shown in fig. 7 to 8, the thermal conductivity analysis of the copper powder and samples a, b, c, and d was performed.
FIG. 7 is a line graph showing the variation of thermal conductivity between 25 ℃ and 300 ℃ for copper powder and samples a, b, c, and d. As can be seen from the figure, the thermal conductivity of the Ni-modified graphene reinforced copper-based composite material is superior to that of pure copper, and the thermal conductivity is high or low with the increase of heating temperature and is distributed in a broken line manner. When a small amount of graphene is added, the thermal conductivity of the sample is obviously improved, wherein the thermal conductivity of the sample c is the best, and the thermal conductivity of the composite material is not obviously reduced along with the increase of the temperature. FIG. 5 shows the thermal conductivity change of copper powder and samples a, b, c, and d at 25 ℃ and 300 ℃ at a temperature rise rate of 2 DEG/min in an Ar atmosphere. It can be seen from the figure that the thermal conductivity of the sample is related to the addition amount of graphene, and the thermal conductivity of the sample is increased before decreased with the increase of the addition amount of graphene, which are all superior to the thermal conductivity of copper under the same process conditions, and the addition of graphene is helpful for improving the thermal conductivity of the material. The heating temperature is 300 ℃, the thermal conductivity of the sample c is 330W/(m × K), the thermal conductivity of pure copper is 273W/(m × K), the improvement is 21% compared with that of pure copper, the thermal conductivity improvement of the composite material at low temperature (namely normal temperature) is smaller than that at high temperature (300 ℃), and the addition of the Ni modified graphene is favorable for improving the high-temperature thermal conductivity of the sample.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A preparation method of a high-conductivity nickel-modified graphene/copper composite material is characterized by comprising the following steps:
loading nickel on graphene by using a two-step hydrothermal method to prepare Ni-Gr powder;
mixing the Ni-Gr powder prepared in the step I with copper powder and performing ball milling to obtain mixed powder;
and step three, sintering the mixed powder prepared in the step two to obtain the nickel modified graphene/copper composite material.
2. The preparation method of the highly conductive nickel-modified graphene/copper composite material according to claim 1, wherein the step (i) specifically comprises the following steps:
a, preparing graphene dispersion liquid, adding a nickel salt solution and a precipitator into the graphene dispersion liquid, and stirring to prepare a solution A;
b, preserving the heat of the solution A prepared in the step a at high temperature, and extracting a precipitate, namely the precipitate A;
and c, dispersing the precipitate A obtained in the step B in deionized water, adding a reducing agent, heating at constant temperature by a hydrothermal method, taking the precipitate, marking as a precipitate B, drying the precipitate B, and grinding to obtain Ni-Gr powder.
3. The method for preparing the highly conductive nickel-modified graphene/copper composite material according to claim 2, wherein the nickel salt does not contain any element except H, O, C, Ni, and the precipitating agent does not contain any element except H, O, C, Ni.
4. The method for preparing the highly conductive nickel-modified graphene/copper composite material according to claim 3, wherein the nickel salt is nickel acetate, and the precipitant is urea.
5. The method for preparing the highly conductive nickel-modified graphene/copper composite material according to claim 2, wherein the reducing agent is one of potassium borohydride and sodium borohydride.
6. The preparation method of the highly conductive nickel-modified graphene/copper composite material according to claim 1, wherein the sintering manner of spark plasma is adopted in the third step.
7. The preparation method of the highly conductive nickel-modified graphene/copper composite material according to any one of claims 1 to 5, which comprises the following specific steps:
weighing 40x mg of graphene, and dispersing in absolute ethyl alcohol for 30min by ultrasonic treatment to obtain a graphene dispersion liquid; weighing x-2 x mmol (CH)3COO)2Ni、0.5x～x mmol CON2H4Dissolving the graphene dispersion liquid in deionized water, mixing the graphene dispersion liquid obtained in the step 1 with the deionized water, and stirring for 5-20 min to obtain a solution A;
b, putting the solution A obtained in the step a into a polytetrafluoroethylene reaction kettle, heating for 4-9 hours at 140-200 ℃, centrifugally washing until the supernatant is transparent, and taking the precipitate as precipitate A;
and c, dispersing the precipitate A prepared in the step B into deionized water, dropwise adding 0.5-2 mol/L potassium borohydride solution into the deionized water, stirring for 5-20 min, heating for 5-12 h at 130-220 ℃, centrifugally washing until supernatant is clear, taking the precipitate, marking as precipitate B, drying the precipitate B at 40-90 ℃ for 18-48 h, and grinding to obtain Ni-Gr powder.
8. The preparation method of the high-conductivity nickel-modified graphene/copper composite material according to any one of claims 1 to 7, wherein the mass fraction of the nickel-modified graphene in the composite material is more than 0 and less than or equal to 0.3 wt%.
9. The method for preparing the highly conductive nickel-modified graphene/copper composite material according to claim 8, wherein the mass fraction w of the nickel-modified graphene in the composite material is 0.2 wt%.
10. A high-conductivity nickel-modified graphene/copper composite material, which is prepared by using the preparation method of the high-conductivity nickel-modified graphene/copper composite material as claimed in any one of claims 1 to 9.
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