CN110923679A - A kind of graphene-loaded nano-copper particle composite material and preparation method thereof - Google Patents
A kind of graphene-loaded nano-copper particle composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110923679A CN110923679A CN201911220662.9A CN201911220662A CN110923679A CN 110923679 A CN110923679 A CN 110923679A CN 201911220662 A CN201911220662 A CN 201911220662A CN 110923679 A CN110923679 A CN 110923679A
- Authority
- CN
- China
- Prior art keywords
- graphene
- solution
- copper
- composite material
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 239000010949 copper Substances 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 73
- 239000002245 particle Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001868 water Inorganic materials 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000007747 plating Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 19
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 5
- 230000008313 sensitization Effects 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- 239000008098 formaldehyde solution Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract description 4
- 238000007772 electroless plating Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
一种石墨烯负载纳米铜颗粒复合材料及其制备方法，复合材料由石墨烯片层及其表面的化学镀层构成，化学镀层为面心立方结构纳米铜；制备方法为：(1)将石墨烯浸入水中超声分散，然后放入敏化液中，在90～100℃敏化处理；(2)将敏化石墨烯取出水洗，然后置于放入活化液中搅拌活化处理，获得活化石墨烯；(3)将活化石墨烯取出水洗，然后置于含有主盐和还原剂成分的镀液中；(4)将镀液升温后调节pH值保温；(5)镀铜石墨烯水洗烘干。本发明的方法可实现石墨烯与纳米铜颗粒之间的稳固结合；石墨烯表面缺陷得到修复，改善石墨烯的综合性能。A graphene-loaded nano-copper particle composite material and a preparation method thereof, the composite material is composed of a graphene sheet layer and an electroless plating layer on the surface thereof, and the electroless plating layer is a face-centered cubic structure nano-copper; the preparation method is: (1) graphene Immerse in water for ultrasonic dispersion, then put it into a sensitizing solution, and conduct sensitization treatment at 90 to 100 °C; (2) take out the sensitized graphene for washing, and then place it in an activation solution for stirring and activation treatment to obtain activated graphene; (3) the activated graphene is taken out and washed, and then placed in the plating solution containing the main salt and the reducing agent composition; (4) after the plating solution is heated up, the pH value is adjusted to keep warm; (5) the copper-plated graphene is washed and dried. The method of the invention can realize the stable combination between the graphene and the nano copper particles; the surface defects of the graphene are repaired, and the comprehensive performance of the graphene is improved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a graphene loaded nano copper particle composite material and a preparation method thereof.
Technical Field
In recent years, the requirements for material performance in the fields of machinery, electronic information, energy storage, aerospace and the like are higher and higher, and the research of high-performance and multipurpose composite materials becomes a hotspot in the field of material research; the copper-based composite material has excellent heat conduction and electric conduction performance, is widely applied to the industrial fields of electronics, electricity, mechanical manufacturing, construction, national defense and the like, and becomes one of important varieties and research hotspots in the field of metal-based composite materials.
The graphene is SP2The thickness of the two-dimensional monolayer atomic crystal material with the hexagonal honeycomb structure formed by closely packing carbon atoms is only 0.3345nm, the material is the thinnest two-dimensional material at present, and the material is also used for constructing SP (SP) such as fullerene, carbon nano tube, graphite and the like2A base component of a hybrid carbon allotrope material; due to the unique structure of the graphene, the graphene has extremely excellent conductivity, mechanical property, heat conductivity and ultrahigh specific surface area, is an ideal reinforcement of a composite material, and has wide application prospects in the aspects of energy storage materials, high-toughness materials, nano materials, friction materials and the like. Therefore, the preparation of the graphene/copper composite material can obviously improve the comprehensive performance of the copper-based composite material and expand the application field of the copper-based composite material.
The graphene/metal composite materials are mainly divided into two main categories, namely graphene-loaded nano metal particle composite materials and graphene-reinforced metal matrix composite materials. Nano metal particles are receiving more and more attention due to their unique optical, electrical and catalytic properties. However, the nano metal particles are very easy to agglomerate due to the extremely high surface energy, and cannot be uniformly dispersed in the matrix in the preparation process of the composite material. Due to the unique two-dimensional planar lamellar structure, the extremely high specific surface area and the surface wrinkles of the graphene, the graphene becomes an ideal carrier for loading inorganic nanoparticles, and can effectively prevent the agglomeration of nano metal particles.
Due to the particularity of the preparation method, the redox graphene has more structural defects and oxygen-containing functional groups on the surface of the graphene, and the performance of the graphene can be reduced due to the defects and the oxygen-containing functional groups; due to the extremely poor wettability between the metal copper and the graphene, no diffusion or reaction exists between adjacent interfaces of the graphene and the metal copper, the interface between the graphene and the copper is difficult to bond, the bonding force of the interface is weak, and the performance of the composite material is seriously influenced.
Disclosure of Invention
Aiming at the problems in the existing graphene metal composite material preparation technology, the invention provides a graphene loaded nano copper particle composite material and a preparation method thereof, and the stable combination of copper and graphene is realized through sensitization and activation treatment.
The graphene-loaded nano-copper particle composite material is of a sheet structure and is composed of a graphene sheet layer and a chemical coating on the surface of the graphene sheet layer, wherein the chemical coating is a copper coating, the copper coating is nano-copper particles with a face-centered cubic structure, and the particle size of the nano-copper particles is 30-200 nm.
The graphene-loaded nano copper particle composite material comprises 14-40% by mass of graphene and the balance of a copper coating.
The preparation method of the graphene loaded nano-copper particle composite material comprises the following steps:
(1) immersing graphene in water, performing ultrasonic dispersion treatment on the graphene, taking out the graphene, putting the graphene into a sensitizing solution, and performing sensitization treatment for 5-10 min at 90-100 ℃ to obtain sensitized graphene; the sensitizing solution is composed of SnCl2The solution is mixed with hydrochloric acid to form SnCl2The concentration of the solution is 10-30 g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.01-0.03;
(2) taking out the sensitized graphene, washing with water until the washing liquid is neutral, then placing the sensitized graphene into an activating solution, and activating for 4-10 min under the stirring condition to obtain activated graphene; the activating solution is prepared from AgNO3Preparation of solution and aqueous ammonia, AgNO3The concentration of the solution is 1-2 g/L, and the dosage of ammonia water is determined according to NH in the activation solution3·H2O and AgNO3Is 2;
(3) taking out the activated graphene, washing with water until the washing liquid is neutral, and then placing in a plating solution; the plating solution is prepared by adding main salt CuSO4·5H2O, reducing agent formaldehyde solution, complexing agent EDTA.2Na and complexing agent C4H4KNaO6And stabilizer 2, 2-bipyridine in water, CuSO4·5H2The dosage of O is 12.5-37.5 g/L of water, the dosage of the formaldehyde solution is 16-48 mL/L of water, the dosage of EDTA-2 Na is 20-60 g/L of water, and C4H4KNaO6The dosage of the 2, 2-bipyridine is 10-30 g/L of water, and the dosage of the 2, 2-bipyridine is 1-3 g/L of water;
(4) heating the plating solution to 35-45 ℃ under the stirring condition, then dropwise adding NaOH solution to adjust the pH value to 12-13, and then preserving heat for 30-40 min to form copper-plated graphene in the plating solution;
(5) and washing the copper-plated graphene until the washing liquor is neutral, and then drying to remove water to prepare the graphene-loaded nano copper particle composite material.
In the step (1), the ultrasonic frequency during ultrasonic dispersion treatment is 35-53 kHz; the ultrasonic treatment time is 10-30 min.
In the step (1), when the graphene is immersed in water, the solid-to-liquid ratio of the graphene to the water is 1.5-2.5 g/L.
In the step (5), the temperature of vacuum drying is 100 +/-2 ℃, and the time is 1-3 h.
The mass concentration of the hydrochloric acid is above 36%.
The mass concentration of the formaldehyde solution is 37-40%.
The above NaOH solution had a concentration of 1M.
Compared with the prior art, the invention has the following characteristics and positive effects:
(1) the surface of the graphene can be uniformly covered with a copper coating without exposed graphene, the nano copper particles are uniformly distributed on the copper coating, and the graphene and the nano copper particles are compounded through the copper coating, so that the graphene and the nano copper particles can be stably combined;
(2) the oxygen-containing functional groups on the surface of the redox graphene are reduced in the chemical plating process, the surface structure defects can be repaired to a certain extent, the graphene structure is more complete, and the comprehensive performance of the graphene is improved;
(3) the preparation method is simple in process, rapid and efficient, and the prepared graphene loaded nano-copper particle composite material is expected to be independently applied to the field of solid lubrication and can also be used as a reinforcement material to prepare a novel composite material; the specific gravity of the material can be increased due to the attachment of copper on the surface of the graphene, the problem of poor wettability between the graphene and the metal matrix can be effectively solved, and the dispersibility of the graphene in the matrix is improved.
Drawings
Fig. 1 is an SEM photograph of a graphene-supported nano-copper particle composite material prepared in example 1 of the present invention;
fig. 2 is an SEM photograph of the graphene-supported nano-copper particle composite material prepared in example 2 of the present invention;
fig. 3 is an XRD pattern of the graphene-supported nano-copper particle composite material and graphene prepared in example 2 of the present invention; in the figure, the upper part is the graphene loaded nano copper particle composite material, and the lower part is the graphene;
fig. 4 is a Raman chart of the graphene-supported nano copper particle composite material and graphene prepared in example 2 of the present invention, wherein ▲ is the graphene-supported nano copper particle composite material, and ● is graphene;
fig. 5 is an FTIR plot of graphene-supported nanocopper particle composites and graphene prepared in example 2 of the present invention; in the figure, graphene is arranged on the upper part, and the graphene loaded nano copper particle composite material is arranged on the lower part;
fig. 6 is an SEM photograph of the graphene-supported nano copper particle composite material prepared in example 3 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The device used for observing the microscopic morphology in the embodiment of the invention is an Ultra Plus type field emission scanning electron microscope.
The apparatus used for the phase analysis in the examples of the present invention was a powder X-ray diffractometer model PANalytical X' Pert Pro.
The equipment adopted for infrared spectroscopic analysis in the embodiment of the invention is an Agilent-660FTIR type FTIR analyzer.
The equipment adopted for Raman spectrum analysis in the embodiment of the invention is an HR800 Raman spectrometer.
The graphene adopted in the embodiment of the invention is commercially available redox graphene.
All chemical reagents used in the examples of the present invention were commercially available analytical reagents.
The water used in the embodiment of the invention is deionized water.
In the embodiment of the invention, a vacuum drying oven is adopted for drying.
The ultrasonic frequency during ultrasonic dispersion treatment in the embodiment of the invention is 35-53 kHz.
The mass concentration of the ammonia water in the embodiment of the invention is more than 25%.
In the embodiment of the invention, the mass concentration of the formaldehyde solution is 37-40%.
Example 1
Immersing graphene in water, and carrying out ultrasonic dispersion treatment on the graphene for 10min, wherein the solid-liquid ratio of the graphene to the water is 2 g/L; then taking out the graphene, putting the graphene into a sensitizing solution, and carrying out sensitization treatment for 10min at 90 ℃ to obtain sensitized graphene;
the sensitizing solution is composed of SnCl2The solution is mixed with hydrochloric acid to form SnCl2The concentration of the solution is 10g/L, the mass concentration of hydrochloric acid is more than 36%, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.01;
taking out the sensitized graphene, washing with water until the washing liquid is neutral, then placing the sensitized graphene into an activating solution, and activating for 4min under the condition of stirring to obtain activated graphene;
the activating solution is AgNO3Silver ammonia solution, AgNO, from solution and ammonia water3The concentration of the solution is 1g/L, and the dosage of ammonia water is NH3·H2O and AgNO3Is 2;
adding main salt CuSO4·5H2O, reducing agent formaldehyde solution, complexing agent EDTA.2Na and complexing agent C4H4KNaO6And stabilizer 2, 2-dipyridine are dissolved in water to prepare plating solution; CuSO4·5H2The dosage of O is 12.5g/L of water, the dosage of the formaldehyde solution is 16mL/L of water, the dosage of EDTA-2 Na is 20g/L of water, C4H4KNaO6The dosage of the water is 10g/L, 2The amount of bipyridine used is 1g/L of water;
taking out the activated graphene, washing with water until the washing liquid is neutral, and then placing in a plating solution;
heating the plating solution to 35 ℃ under the condition of stirring, then dropwise adding NaOH solution to adjust the pH value to 13, and then preserving the temperature for 30min to form copper-plated graphene in the plating solution;
washing copper-plated graphene until washing liquor is neutral, and then drying at 100 +/-2 ℃ for 1h to remove water to prepare the graphene-loaded nano copper particle composite material; the graphene-loaded nano-copper particle composite material is of a sheet structure and is composed of a graphene sheet layer and a chemical coating on the surface of the graphene sheet layer, wherein the chemical coating is a copper coating, the copper coating is nano-copper particles with a face-centered cubic structure, and the particle size of the nano-copper particles is 30-80 nm; wherein the mass percent of the graphene is 40%, and the balance is a copper plating layer; the SEM photograph is shown in FIG. 1.
Example 2
The method is the same as example 1, except that:
(1) performing ultrasonic dispersion treatment for 30min, wherein the solid-to-liquid ratio of graphene to water is 2.5 g/L; sensitizing at 95 deg.C for 8 min;
(2)SnCl2the concentration of the solution is 20g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.02;
(3) activating for 7 min; AgNO used for activating liquid3The concentration of the solution is 1.5 g/L;
(4) CuSO for preparing plating solution4·5H2The dosage of O is 25g/L of water, the dosage of the formaldehyde solution is 32mL/L of water, the dosage of EDTA-2 Na is 40g/L of water, C4H4KNaO6The dosage of the 2, 2-bipyridyl is 20g/L of water, and the dosage of the 2, 2-bipyridyl is 2g/L of water;
(5) heating the plating solution to 40 ℃, dropwise adding NaOH solution to adjust the pH value to 12.5, and then keeping the temperature for 35 min;
(6) drying for 2h at 100 +/-2 ℃; 29% of graphene in the graphene-loaded nano-copper particle composite material by mass; the particle size of the nano copper particles is 30-200 nm, and an SEM photograph is shown in figure 2;
the XRD contrast of the graphene and graphene supported nano-copper particle composite material is shown in fig. 3; as can be seen from the figure, the drawing,an impurity C peak with a non-graphene structure exists on the surface of the graphene; the impurity C peak on the surface of the composite material is obviously weakened, the characteristic peak intensity of the copper crystal is large, the existence of copper is proved, and the diffraction peak width is widened due to the nanoscale copper particles; at the same time, Cu appears on the surface due to oxidation of copper and the like2A characteristic peak of O;
the Raman spectrum of the graphene and graphene loaded nano copper particle composite material is shown in fig. 4; in Raman spectroscopy of graphene, the intensity ratio (I) of the D peak and the G peak is generally usedD/IG) Characterizing structural defects of graphene, ID/IGThe smaller the value, the lower the defect density; by the pair ID/IGCalculating to obtain the result that the graphene is chemically plated ID/IGThe defect density of the graphene surface can be reduced from 1.367 to 1.187, which shows that the defect density of the graphene surface can be reduced through electroless plating; by analyzing the structures of the graphene before and after chemical plating through Raman spectroscopy, the chemical plating on the surface of the graphene not only has no influence on the inherent structure of the graphene and has no new defect introduced, but also has certain repair on the defect on the surface of the graphene, and can effectively reduce the defect concentration on the surface of the graphene;
the FTIR spectrum of the graphene and graphene supported nano-copper particle composite material is shown in fig. 5; oxygen-containing functional groups such as C-O, C-O, O-H exist on the surface of the graphene, after chemical plating, the strength of the oxygen-containing functional groups is obviously reduced, and characteristic peaks of partial oxygen-containing functional groups disappear, so that the repairing effect of the chemical plating process on the surface defects of the graphene is further explained.
Example 3
The method is the same as example 1, except that:
(1) performing ultrasonic dispersion treatment for 20min, wherein the solid-to-liquid ratio of graphene to water is 1.5 g/L; sensitizing at 100 deg.C for 5 min;
(2)SnCl2the concentration of the solution is 30g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.03;
(3) activating for 10 min; AgNO used for activating liquid3The concentration of the solution is 2 g/L;
(4) CuSO for preparing plating solution4·5H2Use of O37.5g/L of water, 48mL/L of water as formaldehyde solution, 60g/L of water as EDTA-2 Na and C4H4KNaO6The dosage of the 2, 2-bipyridyl is 30g/L of water, and the dosage of the 2, 2-bipyridyl is 3g/L of water;
(5) heating the plating solution to 45 ℃, dropwise adding NaOH solution to adjust the pH value to 12, and then preserving the temperature for 40 min;
(6) drying for 3h at 100 +/-2 ℃; the mass percent of graphene in the graphene-loaded nano-copper particle composite material is 14%; the particle size of the nano-copper particles is 30-40 nm, and the SEM photograph is shown in figure 6.
Claims (8)
1. The graphene-loaded nano-copper particle composite material is characterized by comprising a graphene sheet layer and a chemical coating on the surface of the graphene sheet layer, wherein the chemical coating is a copper coating, the copper coating is nano-copper particles with a face-centered cubic structure, and the particle size of the nano-copper particles is 30-200 nm.
2. The graphene-supported nano-copper particle composite material as claimed in claim 1, wherein the graphene-supported nano-copper particle composite material comprises 14-40% by mass of graphene, and the balance of copper plating.
3. The preparation method of the graphene-supported nano copper particle composite material of claim 1 is characterized by comprising the following steps:
(1) immersing graphene in water, performing ultrasonic dispersion treatment on the graphene, taking out the graphene, putting the graphene into a sensitizing solution, and performing sensitization treatment for 5-10 min at 90-100 ℃ to obtain sensitized graphene; the sensitizing solution is composed of SnCl2The solution is mixed with hydrochloric acid to form SnCl2The concentration of the solution is 10-30 g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.01-0.03;
(2) taking out the sensitized graphene, washing with water until the washing liquid is neutral, then placing the sensitized graphene into an activating solution, and activating for 4-10 min under the stirring condition to obtain activated graphene; the activating solution is prepared from AgNO3Preparation of solution and aqueous ammonia, AgNO3The concentration of the solution is 1-2 g/L, and the dosage of ammonia water is NH3·H2O and AgNO3Is 2;
(3) taking out the activated graphene, washing with water until the washing liquid is neutral, and then placing in a plating solution; the plating solution is prepared by adding main salt CuSO4·5H2O, reducing agent formaldehyde solution, complexing agent EDTA.2Na and complexing agent C4H4KNaO6And stabilizer 2, 2-bipyridine in water, CuSO4·5H2The dosage of O is 12.5-37.5 g/L of water, the dosage of the formaldehyde solution is 16-48 mL/L of water, the dosage of EDTA-2 Na is 20-60 g/L of water, and C4H4KNaO6The dosage of the 2, 2-bipyridine is 10-30 g/L of water, and the dosage of the 2, 2-bipyridine is 1-3 g/L of water;
(4) heating the plating solution to 35-45 ℃ under the stirring condition, then dropwise adding NaOH solution to adjust the pH value to 12-13, and then preserving heat for 30-40 min to form copper-plated graphene in the plating solution;
(5) and washing the copper-plated graphene until the washing liquor is neutral, and then drying to remove water to prepare the graphene-loaded nano copper particle composite material.
4. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein in the step (1), the ultrasonic frequency during ultrasonic dispersion treatment is 35-53 kHz; the ultrasonic treatment time is 10-30 min.
5. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein in the step (1), when the graphene is immersed in water, the solid-to-liquid ratio of the graphene to the water is 1.5-2.5 g/L.
6. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein in the step (5), the temperature of vacuum drying is 100 +/-2 ℃ and the time is 1-3 h.
7. The method for preparing a graphene-supported nano copper particle composite material according to claim 3, wherein the mass concentration of the hydrochloric acid is 36% or more.
8. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein the mass concentration of the formaldehyde solution is 37-40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911220662.9A CN110923679A (en) | 2019-12-03 | 2019-12-03 | A kind of graphene-loaded nano-copper particle composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911220662.9A CN110923679A (en) | 2019-12-03 | 2019-12-03 | A kind of graphene-loaded nano-copper particle composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110923679A true CN110923679A (en) | 2020-03-27 |
Family
ID=69847237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911220662.9A Pending CN110923679A (en) | 2019-12-03 | 2019-12-03 | A kind of graphene-loaded nano-copper particle composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110923679A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111593226A (en) * | 2020-06-16 | 2020-08-28 | 江西省科学院应用物理研究所 | Graphene/copper composite material and preparation method thereof |
| CN111690324A (en) * | 2020-07-21 | 2020-09-22 | 宁波计氏金属新材料有限公司 | Corrosion-resistant chromium-free coating and surface treatment process thereof |
| CN112624096A (en) * | 2020-12-23 | 2021-04-09 | 西安交通大学 | Graphene surface dispersibility modification method |
| CN115896880A (en) * | 2022-11-23 | 2023-04-04 | 山东大学 | A method for preparing nano-copper/graphene composite coating by pulse electric brush plating technology |
| CN116851748A (en) * | 2023-07-19 | 2023-10-10 | 西南交通大学 | Nano-metal particle modified graphene enhanced conductivity-reinforced copper-based composite material and its high temperature and high pressure preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451227A (en) * | 2014-12-10 | 2015-03-25 | 济南大学 | Preparation method of copper-plated graphene reinforced metal-based composite |
| CN106480434A (en) * | 2015-08-26 | 2017-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of chemical plating Graphene and preparation method thereof and a kind of metal-base composites |
-
2019
- 2019-12-03 CN CN201911220662.9A patent/CN110923679A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451227A (en) * | 2014-12-10 | 2015-03-25 | 济南大学 | Preparation method of copper-plated graphene reinforced metal-based composite |
| CN106480434A (en) * | 2015-08-26 | 2017-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of chemical plating Graphene and preparation method thereof and a kind of metal-base composites |
Non-Patent Citations (1)
| Title |
|---|
| 卢晓通等: ""石墨烯/铜复合材料的制备与摩擦性能测试"", 《中国有色金属学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111593226A (en) * | 2020-06-16 | 2020-08-28 | 江西省科学院应用物理研究所 | Graphene/copper composite material and preparation method thereof |
| CN111690324A (en) * | 2020-07-21 | 2020-09-22 | 宁波计氏金属新材料有限公司 | Corrosion-resistant chromium-free coating and surface treatment process thereof |
| CN112624096A (en) * | 2020-12-23 | 2021-04-09 | 西安交通大学 | Graphene surface dispersibility modification method |
| CN115896880A (en) * | 2022-11-23 | 2023-04-04 | 山东大学 | A method for preparing nano-copper/graphene composite coating by pulse electric brush plating technology |
| CN115896880B (en) * | 2022-11-23 | 2024-06-04 | 山东大学 | A method for preparing nano copper/graphene composite coating using pulse brush plating technology |
| CN116851748A (en) * | 2023-07-19 | 2023-10-10 | 西南交通大学 | Nano-metal particle modified graphene enhanced conductivity-reinforced copper-based composite material and its high temperature and high pressure preparation method |
| CN116851748B (en) * | 2023-07-19 | 2024-02-09 | 西南交通大学 | Modified graphene conductivity-enhanced copper-based composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110923679A (en) | A kind of graphene-loaded nano-copper particle composite material and preparation method thereof | |
| CN102002652B (en) | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof | |
| CN113831131B (en) | Carbon foam in-situ growth carbon nanotube composite electromagnetic shielding material and preparation method thereof | |
| CN109852835B (en) | A kind of preparation method of graphene/copper nanocomposite | |
| CN112164795B (en) | Preparation method of silver nanoparticle-carbon nanotube composite material | |
| CN106563484B (en) | Preparation method of mesoporous hollow nitrogen-doped carbon-coated copper nanocatalyst | |
| CN101781757A (en) | Method for chemically plating nano nickel particles on surface of multi-wall carbon nano tube without using palladium | |
| CN108213456A (en) | A kind of preparation method of cube copper nanoparticle | |
| CN105665735A (en) | Solvothermal method for preparing nitrogen-doped graphene-gold nanoparticle composite through single step | |
| CN109338134A (en) | A kind of preparation method of nickel-plated carbon nanotube reinforced aluminum matrix composite material | |
| CN111905796A (en) | Preparation method of superfine metal nanoparticle/carbon nitride nanosheet composite material | |
| CN102441668B (en) | Method for preparing Fe/Al micro-nano composite powder | |
| CN109295335B (en) | A kind of modified expanded graphite-graphite/copper composite material and preparation method thereof | |
| CN112429722A (en) | Nano metal particle doped graphene film and preparation method thereof | |
| CN110577209A (en) | Preparation method of in-situ synthesis of carbon nanotube surface-supported copper oxide nanoparticles | |
| CN105375041A (en) | Carbon nanotube-transition metal-carbon fiber composite material and preparation method and application therefor | |
| CN106735299A (en) | A kind of graphene microchip loads the preparation method of nanometer nickle composite powder | |
| CN100355939C (en) | Method for cladding honeycomb metal cobalt or cobalt alloy on nickel or nickel alloy powder surface | |
| CN112008087A (en) | Method for improving comprehensive performance of carbon nano material reinforced nickel-based high-temperature alloy | |
| CN114561805B (en) | Flexible electromagnetic shielding material and preparation method thereof | |
| CN101147978A (en) | Preparation of needle-shaped nickel nanoparticles by microwave-assisted liquid phase reduction | |
| CN105209660A (en) | Method for coating of carbon nanomaterials | |
| CN106554009A (en) | A kind of preparation method of nitrogen-doped graphene load gold nano particle | |
| Dingsheng et al. | Electroless deposition of Cu on multiwalled carbon nanotubes | |
| CN109524645B (en) | Method for preparing tin/copper/carbon composite material with assistance of chelating agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200327 |