CN106086979A - Graphene/metal composite material and preparation method thereof - Google Patents
Graphene/metal composite material and preparation method thereof Download PDFInfo
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- CN106086979A CN106086979A CN201610430944.1A CN201610430944A CN106086979A CN 106086979 A CN106086979 A CN 106086979A CN 201610430944 A CN201610430944 A CN 201610430944A CN 106086979 A CN106086979 A CN 106086979A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002905 metal composite material Substances 0.000 title abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 79
- 239000010439 graphite Substances 0.000 claims abstract description 79
- 238000004070 electrodeposition Methods 0.000 claims abstract description 31
- 239000007769 metal material Substances 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- 239000001117 sulphuric acid Substances 0.000 claims description 12
- 235000011149 sulphuric acid Nutrition 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- -1 weigh Chemical compound 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
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- 238000003828 vacuum filtration Methods 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 2
- 230000017525 heat dissipation Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 239000011889 copper foil Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- 239000010949 copper Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 229910000471 manganese heptoxide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 241000238370 Sepia Species 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GMYSDEOJMBLAKZ-UHFFFAOYSA-N calcium indium Chemical compound [Ca].[In] GMYSDEOJMBLAKZ-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
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- 229960004756 ethanol Drugs 0.000 description 1
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- 239000007770 graphite material Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene/metal composite material, which comprises the following steps: obtaining graphite oxide, and preparing a graphene oxide dispersion system by using the graphite oxide; obtaining a metal material, and cleaning the metal material; preparing an electrodeposition solution for preparing the graphene/metal composite material by using a graphene oxide dispersion system; setting parameters of an electro-deposition device, placing the electro-deposition solution and the metal material in the electro-deposition device, and electrifying to obtain the graphene/metal composite material. According to the invention, the graphene/metal composite material with high heat dissipation performance, oxidation resistance and good hydrophobicity can be efficiently and environmentally prepared through a simple and easily-built experimental device.
Description
Technical field
The present invention relates to field of compound material, particularly relate to a kind of Graphene/metallic composite and preparation method thereof.
Background technology
Electronic technology is fast-developing in recent years, and electronic component volume constantly reduces, and circuit chip integrated level is continuously increased.Greatly
Power electronic element can produce substantial amounts of heat, if not taking effective cooling measure, heat sheds not in time, can reduce the device longevity
Life, affects equipment job stability simultaneously.Generally utilize radiator that the heat of power device is dispersed into surrounding space.But,
Heat abstractor to take the biggest volume.In the application scenario that some are special, it is desirable to electronic device power is big, the body taken simultaneously
Long-pending little.This is accomplished by reducing radiator volume, ensures reliable heat dispersion simultaneously.
Current heat sink material is mainly aluminum alloy sheet, but the heat conductivity of aluminum is relatively low, and the heat conductivity of gold, silver is higher
But cost is the highest, be not suitable for application for heat sink material.The heat conductivity of copper is 398W/m K, but uses merely metallic copper to lead
Hot material, the problem of oxidation of copper is difficult to solve, and metal has hydrophilic, there is hidden danger as heat sink material.The most a large amount of
Be applied to the heat radiations such as telecommunications industry, notebook, mobile phone is graphite heat radiation fin.Current graphite heat radiation fin manufacture method is mainly
Polymeric membrane is heated to 1000 DEG C of high temperature cabonizations, more additional calendering technology is made, preparation process complex process, time-consumingly consume
Power, wastes mass energy, relatively costly；It addition, aspect of performance, the heat conductivity of graphite material is planar up to 150-
1500W/m K, compared to Graphene heat conductivity 5300W/m K, inferior much.
Summary of the invention
The technical problem that present invention mainly solves is to provide a kind of Graphene/metallic composite and preparation method thereof, energy
Enough by experimental provision easy, that easily build efficiently, environmental protection prepared to have high heat dispersion, non-oxidizability and hydrophobicity good
Graphene/metallic composite.
For solving above-mentioned technical problem, the technical scheme that the present invention uses is: provide a kind of Graphene/metal composite
The preparation method of material, including: obtain graphite oxide, utilize graphite oxide to prepare graphene oxide dispersion；Obtain metal
Material, and metal material is cleaned；Utilize graphene oxide dispersion, be configured to prepare Graphene/metal composite
The electric depositing solution of material；Electrodeposition apparatus parameter is set, electric depositing solution and metal material are placed in electrodeposition apparatus, energising
Rear prepared Graphene/metallic composite.
For solving above-mentioned technical problem, the technical scheme that the present invention uses is: provide a kind of Graphene/metal composite
Material, this Graphene/metallic composite is the preparation side by the Graphene/metallic composite described in preceding solution
Method prepares.
Being different from prior art, the preparation method of the Graphene/metallic composite of the present invention makes oxidized graphite into oxygen
Functionalized graphene dispersion, is configured to electric depositing solution, is together positioned over electricity with electric depositing solution heavy after being cleaned by metal material
In long-pending equipment, set energising reaction after the parameter of electrodeposition apparatus, prepare the Graphene/metal for electronic equipment dissipating heat multiple
Condensation material, can realize the control of Graphene deposit thickness by changing electrochemical parameter, can be by changing metal material
Apparent condition realizes oriented growth Graphene, can realize the control of deposited graphite alkene quality by changing solution concentration.Pass through
The present invention, it is possible to, the prepared Graphene/metallic composite of environmental protection efficient by experimental provision easy, that easily build.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preparation method of a kind of Graphene/metallic composite that the present invention provides；
Fig. 2 be this present invention provide a kind of Graphene/metallic composite preparation method in solid oxidation graphite
Alkene carries out the diffracting spectrum of X-ray diffraction；
Fig. 3 be a kind of Graphene/metallic composite that the present invention provides preparation method in by graphene oxide electricity
Deposition prepares the cyclic voltammetry curve of Graphene/metallic composite.
Detailed description of the invention
Make to describe in more detail further to technical scheme below in conjunction with detailed description of the invention.Obviously, retouched
The embodiment stated is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained on the premise of not making creative work, all should belong to
The scope of protection of the invention.
Graphene is that carbon atom is with sp2New Two Dimensional (2D) atomic crystal that the monoatomic layer that hydridization connects is constituted, has
The a series of abundant and physical property of novelty.The exploitation that physics, chemistry and mechanical property are composite of Graphene uniqueness carries
Supply motive power.Graphene is the preferable reinforcement of various composite, it is expected to develop have rich and varied, excellent properties
The composites such as polymer base, Metal Substrate.Within 2010, Nobel laureate Geim thinks, although Graphene takes in many fields
Obtain many breakthroughs, but graphene composite material is to be expected to one of field realizing application the soonest.In recent years, mechanical, electric
The fast developments such as son, track traffic are day by day strong to high-strength, high connductivity (hot) moulding material demand, and pure metals has been difficult to
Meeting and be actually needed, material develops to Composite direction and has become as inexorable trend.Metal material has high heat conduction, conducts electricity and become
Shape performance, is the important matrix material preparing above-mentioned composite, and metal-base composites has become one of study hotspot.But
It is that the graphene composite material being seen in report at present focuses primarily upon Graphene/polymer composites field.Such as, 2006
Year, reported first Graphene/polymer composites, this composite room temperature conductivity went up at " Nature " in Rouff seminar
Up to 0.01S/cm, it is expected to be applied in terms of conductive material.A lot of results of study shows, Graphene (graphene oxide)
Composite many-side performance can be significantly improved as nanocomposite constituents, demonstrate vast potential for future development.But, current state
On border, the report about Graphene/metallic composite is still little, main research focus mostly at Graphene and nano metal and
Being combined of metal-oxide etc., studies its application at aspects such as catalysis, energy storage, rare research worker graphene coated macroscopic view
Metal, the improvement of metallic matrix performance is affected by research Graphene.The main research work of this respect is as follows:
CVD is used to grown Graphene laminated structure in nickel substrate when less than 460 DEG C at Miller in 2010 etc.,
Good at one-dimensional border Graphene and carbide surface phase Lattice Matching, composite property is excellent, has good application prospect.
The Linh T.Le of the Stevens Institute of Technology of the U.S. in 2011 etc. use the principle of inkjet printing to grow on titanium foil
Graphene oxide, the composite then obtained by redox graphene in 200 DEG C of nitrogen environments, chemical property is excellent
Good, can be used as the electrode of ultracapacitor.
The Hongcai Gao etc. of Nanyang Technological University in 2012 have studied and uses electro-deposition on graphene film
The nano cubic structure of method deposition copper, provides another possibility for realizing flexible energy storage device.Jagannadham
K etc. use electrochemical deposition method at copper sheet substrates Cu and Graphene, use CuSO4Electricity is done with graphene oxide mixed solution
Xie Zhi, afterwards at H2The GO that reduces in protective atmosphere prepares the complex of copper and Graphene, and this composite thickness is higher than 200um,
Thermal conductivity improves a lot, and can apply to effective heat radiation of electronic component.Jagannadham K is investigated indium Graphene
Complex and indium calcium graphene complex, and can effectively Control release condition to obtain the different heat of complex
Conductance.
Zhuo Q in 2013 etc., by self-catalyzed reaction at room temperature, have obtained the Graphene/gold of size, morphology controllable
Belonging to nanoparticle, the catalysis activity of this complex is the highest.Li Li, Zhang Jimei etc. use microwave irradiation, with green, nontoxic
Polyethylene Glycol (PEG) is reducing agent and stabilizer, prepares Graphene and metal nanometer composite material thereof in situ, it is achieved that the control of GO
System reduction and the uniform attachment of metal nanoparticle.
Chengbin Liu in 2014 etc. use a step CV electrochemical deposition method to obtain copper and graphene composite material, and
Have studied the reunion situation of Graphene that electro-deposition obtains, the composite obtained has and is preferably catalyzed activity.
Contrast current research work, it can be seen that the research of this respect belongs to science focus, there is wide development empty
Between, utilize the formability of the advantages such as the high intensity of Graphene, high-termal conductivity and metal to be expected to develop and have Good All-around Property
Graphene/metallic composite.
The present invention mainly exploitation Graphene this " star " material, at the potential in metallic composite field, utilizes graphite
The character that alkene is intrinsic, especially its huge specific surface area and high thermal conductivity, select Graphene to do Metal Substrate performance enhancement and be combined
Material, use a step efficiently, the electrochemical deposition method of environmental protection Graphene is combined with bulky metals, play Graphene
Cooperative effect, to obtain the composite of excellent properties, such as grows Graphene, so that composite has on Copper Foil
Bigger thermal conductivity, increases heat radiation, antioxygenic property etc., to be applied to nano-electronic devices, high frequency and high power device (as
Power enhancer, laser diode etc.) etc..
The present invention solves the limitation of Graphene application aspect, it is provided that Graphene quickly, scale application effective
Approach, the method for use has efficiently compared to other application of Graphene, environmental protection, energy-conservation superiority.Graphene oxide at present
Preparation technology comparative maturity, use traditional Hummer ' s method can obtain graphene oxide, the present invention uses
Raw material is the aqueous dispersions of certain density graphene oxide, and raw material can be obtained by prior art.The present invention develops
A kind of under the small voltage effect with Weak current, use certain electrochemical parameter, the oxidation stone that will be in aqueous solution
Ink alkene electrochemical reduction is Graphene, and during reduction, Graphene is deposited on the surface of active metal material, through room temperature
Air-drying the composite of the most available Graphene and metal, this material has heat dispersion and the antioxygenic property etc. of excellence.
Refering to Fig. 1, Fig. 2 and Fig. 3, Fig. 1 is that the preparation method of a kind of Graphene/metallic composite that the present invention provides is real
Execute the schematic flow sheet of mode；Fig. 2 be a kind of Graphene/metallic composite that the present invention provides preparation method in solid
Graphene oxide carries out the diffracting spectrum of X-ray diffraction；Fig. 3 is a kind of Graphene/metallic composite that the present invention provides
Preparation method is prepared the cyclic voltammetry curve of Graphene/metallic composite by graphene oxide electro-deposition.The method
Step includes:
S110: obtain graphite oxide, utilize graphite oxide to prepare graphene oxide dispersion.
In this step, using the Hummers method improved to prepare graphite oxide, the step preparing graphite oxide includes:
S111: prepared by graphite oxide material and pre-oxidizes, neutralized obtaining after drying pre-oxidizes graphite；Wherein,
The material of preparing of graphite oxide at least includes: potassium peroxydisulfate, phosphorus pentoxide and natural flake graphite, and mass ratio is 1:1:2.
In step S111, the step pre-oxidizing the material preparing graphite oxide includes:
S1111: quality potassium peroxydisulfate and the phosphorus pentoxide such as weigh, adds in conical flask, seals with preservative film, measure dense
Sulphuric acid adds in conical flask, adds magneton, puts in the water-bath of 80 DEG C and heats, and seals stirring.
Generally weigh 10g potassium peroxydisulfate and 10g phosphorus pentoxide with electronic scale successively, add in conical flask, use preservative film
Sealing, takes 30ml concentrated sulphuric acid with graduated cylinder and adds in conical flask, add magneton, put in the water-bath of 80 DEG C and heat after sealing, and
Sealing stirring.
S1112: stir and become clarification to solution, continues to add natural flake graphite in solution, stirs, put after sealing
Enter 80 DEG C of thermostatic drying chambers, be allowed to react 6 hours.
After stirring about 30min, solution becomes clarification, continues to add 20g natural flake graphite in the mixed solution of 80 DEG C,
Now have and smolder, stir with Glass rod, put into after sealing mouth with preservative film in thermostatic drying chamber, 80 DEG C of insulation 6h.
S1113: take out conical flask from thermostatic drying chamber and be cooled to room temperature.
S1114: the sample in conical flask carries out vacuum filtration, is washed with deionized until filtrate is neutrality simultaneously,
The pre-oxidation graphite obtained is dried at normal temperatures to constant weight.
After preparing pre-oxidation graphite, enter step S112.
S112: adding concentrated sulphuric acid in pre-oxidation graphite, keep low temperature and be slowly added to potassium permanganate, temperature maintains 10
Insulation reaction is carried out below DEG C；The mass ratio of pre-oxidation graphite and potassium permanganate is 1:3.
In this step, comprise the following steps:
S1121: put into mixture of ice and water in heat-collecting magnetic stirring device, is fixedly installed one or three hole flasks, and adds one
The quantitative pre-oxidation graphite being dried.
In this step, the pre-oxidation graphite that 20g prepares through previous step and is easily dried is removed.
S1122: add concentrated sulphuric acid in three hole flasks, uses the stirring paddle stirring of heat-collecting magnetic stirring device, exists simultaneously
Place thermometer in three hole flasks, be maintained at 0 DEG C controlling three hole pot temperature.
Add 460ml concentrated sulphuric acid (analytical pure), use the stirring paddle stirring of heat-collecting magnetic stirring device, put in three hole flasks
Entering thermometer, keep the temperature at 0 DEG C, now the mixture in three hole flasks shows black.
S1123: weigh the potassium permanganate being three times in pre-oxidation graphite, slowly, is dividedly in some parts three hole flasks, is incubated after adding
React 2 hours, add ice cube to keep temperature less than 10 DEG C to water-bath simultaneously.
Electronic scale weighs 60g potassium permanganate (analytical pure), slowly, is dividedly in some parts in three hole flasks, and feed rate is not to have
Purple gas is emerged and is advisable, and the time controlled about half an hour.Now solution is blackish green.After adding, insulation reaction 2h,
Period adds ice cube to keep temperature less than 10 DEG C in water-bath.
Add potassium permanganate to carry out in ice-water bath, react because potassium permanganate joins in concentrated sulphuric acid, raw
Become volatile green oil thing Mn2O7(generated MnO by thermal explosion2、O2、O3), this be also the present invention preparation process use open
Put the reason of container.Because there being Mn2O7Generation cause mixture during low-temp reaction to be blackish green by black transitions；Reaction
During purple material occurs on three hole shake flask volume walls, be Mn2O7Decompose and produce gas, make permanganic acid volatilize, deposit after cooling
On three hole shake flask volume walls.It is possible to prevent the side reactions such as graphite and strong sulfuric acid response to occur under low temperature environment simultaneously.
S113: slowly heat up, makes temperature step up 35 DEG C with design temperature difference, and maintains temperature to carry out two at 35 DEG C
Secondary insulation reaction.
Previous step starts slowly to heat up after three hole flask insulation 2h, owing to initial temperature is 10 DEG C, just sets 15
DEG C, set a temperature every 3 DEG C, to ensure to be to slowly warm up to 35 DEG C, be incubated 2h at 35 DEG C, until the product in flask is palm fibre
Brown batter shape.
The reaction of this step is referred to as the reaction of middle temperature, is that the process of graphite intercalation, i.e. sulfate ion are inserted by concentrated sulphuric acid
Enter graphite layers, proton is provided simultaneously, to promote the oxidability of potassium permanganate.It is thorough that intercalation is carried out, the mixing in flask
Thing will become mud shape, and liquid disappears, and volume of mixture expands, and now stirring becomes difficulty.
S114: add deionized water, 4 seconds one, temperature is maintained at less than 95 DEG C and reacts；Wherein deionized water and
The volume ratio of concentrated sulphuric acid is 2:1.
Remove water-bath after insulation, use constant pressure funnel to add deionized water 920ml in three hole flasks, 4 seconds one,
Temperature is maintained at less than 95 DEG C, and the mixture in three hole flasks is sepia.Owing to adding substantial amounts of water, concentrated sulphuric acid water suction is put
Heat, it is provided that localized hyperthermia.
S115: reaction solution is poured in the mixed solution of deionized water and hydrogen peroxide, staticly settle, add 10% dilute
Hydrochloric acid solution, stirring, foam washing 24h, continuous three times.
In 5000ml beaker, add 2800ml deionized water and 50ml hydrogen peroxide, be placed on stirring of heat-collecting magnetic stirring device
Mixing and stir under oar, poured in 5000ml beaker by the mixed liquor in three hole flasks, solution becomes glassy yellow, illustrates that graphite obtains
Well oxidation.Mixed liquor stands certain time to be precipitated, and outwells upper liquid, adds the dilute hydrochloric acid solution of 10%, stirring,
Foam washing 24h, continuous three times.
In this step, hydrogen peroxide joins in reaction as reducing agent, reacts with unreacted potassium permanganate completely.By mistake
Hydrogen oxide, as reducing agent, generates water and oxygen, will not pollute product.Now potassium permanganate is consumed completely, reaction
The color of system is glassy yellow by brown stain.
Now complete the preparation to graphite oxide, then utilize graphite oxide to prepare graphene oxide dispersion.
The graphite oxide that improved Hummers method and acid cleaning process obtain, containing more foreign ion (as
SO4 2-Deng), acidity very strong, containing relatively juicy, due to the quantitative requirement of subsequent step, need to configure certain density oxidation stone
Ink alkene solution so that it is further purified, the process such as is dried, for obtain purer oxidation graphite solid with
And protection baking oven acid and alkali corrosion, it is necessary to passing through process to graphite oxide is neutrality.To this end, present invention employs high speed centrifugation
Method and dialysis carry out post processing to the graphite oxide after pickling, and detailed process is as follows:
(1) supercentrifugal process
Through consulting literatures, the sedimentation of graphene oxide can be controlled by regulation pH value, use repeatedly centrifuge washing
Method, settles down neutral graphite oxide, and reduces foreign ion, and then oven drying obtains the solid of graphite oxide.
Concrete operations are as follows.
1. take the appropriate thickness graphite oxide through persalt washing to be placed in beaker, add deionized water, agitation and dilution.
2. taking above-mentioned solution, drip the most at a slow speed certain density NaOH solution, it is steady that regulation pH value breaks graphite oxide
Fixed dispersion so that it is be prone to sedimentation.
3. the solution in step 2 is placed in centrifuge tube, puts into centrifugal 15min in centrifuge, take out and find graphite oxide
Can well settle in alkaline environment, supernatant is relatively clarified, and can directly outwell.It addition, aoxidize when pH value is about 3
Graphite can also preferably settle, and supernatant is glassy yellow.In this explanation supernatant, scattered oxidized graphite flake layer is relatively fine, permissible
Recycling.
4. the lower sediment that will obtain in step 3, adds deionized water wash, recentrifuge, until the supernatant and lower floor
Precipitum is all in neutrality.
5. the neutrality obtained, graphite oxide that concentration is high are made thinner in culture dish, be placed in 40 DEG C of baking ovens and be dried, finally
Obtain the solid of graphite oxide.
Just can weigh after obtaining oxidation graphite solid for configuring certain density graphite oxide solution, through ultrasonic point
Dissipate the solution of 2h (temperature will be less than 40 DEG C) the most available finite concentration graphene oxide, to treat subsequent step uses.
(2) dialysis
Dialysis process graphite oxide be by pickling after graphite oxide, be loaded in bag filter, then immerse deionized water
In, change water twice daily, continuous 7 days, utilize dialyzer that the foreign ion in graphite oxide is gone by the dialyzing of little molecule
Remove.
For the dialyzer bought on market, it be washed.Concrete washing methods is as follows: weigh sodium bicarbonate
(NaHCO3) 20g, ethylenediaminetetraacetic acid (EDTA) 2.9g, measure deionized water 1L and boil, bag filter is put into 100 DEG C go from
In sub-water, after 10min, take out deionized water and clean.It addition, measure 1L deionized water again and boil, add 2.9g EDTA,
Decocting in water 10min, then clean with deionized water.After having dialysed, directly the graphite oxide in bag filter is taken out, be spread out in cultivation
In ware, it is placed in baking oven 40 DEG C and is dried, after being dried, it is possible to for configuring the solution of graphene oxide.
Operate low cost, efficiency of supercentrifugal process is high, but removal effect for foreign ion is strong and also draws
Enter foreign ion such as Na+、Cl-Deng；The GO that dialysis obtains, almost without foreign ion, but has more water, is dried time-consuming long,
Efficiency is low, and cost is high.
The solid oxidation Graphene obtaining dialysis carries out X-ray diffraction, and the diffracting spectrum obtained is as shown in Figure 2.By
This figure understands, and solid oxidation Graphene has spreading out of a diffraction maximum the strongest, i.e. graphite oxide crystal face near 2 θ=11.17 °
Penetrate peak.Graphite oxide peak the most substantially represents that oxidation effectiveness is the best, and relative to solid oxidation Graphene, single crystal graphite is in 2 θ=26 °
Near produce diffraction maximum, but, this figure does not has obvious diffraction maximum in 2 θ=26 °, illustrate the graphite in this material by
Oxidation, generates graphene oxide, so single crystal graphite diffraction maximum disappears.
After completing the preparation that graphite oxide prepares graphene oxide dispersion, enter step S120.
S120: obtain metal material, and metal material is cleaned.
In the present embodiment, metal material uses Copper Foil.In other embodiments, metal material can be selected for tinsel
Such as aluminium wire, copper wire, aluminium foil, rustless steel thin slice etc..Before Copper Foil substrates Graphene, first have to use hydrochloric acid, ethanol and
Acetone carries out precleaning to Copper Foil, and to remove surface and oil contaminant and oxide, specific experiment step is as follows:
S121: preparation deionized water/hydrochloric acid volume ratio is the solution of 1:3, is put into by Copper Foil in solution, uses ultrasound wave clear
Washing machine ultrasonic cleaning 5min.
The thickness of Copper Foil generally chooses any one in 0.040mm, 0.060mm and 0.10mm.
S122: solution is outwelled, and use deionized water rinsing Copper Foil.
S123: add acetone to submergence Copper Foil, use ultrasonic washing unit ultrasonic cleaning 10min, to remove copper foil surface
Oil stain.
S124: outwell acetone, uses deionized water rinsing Copper Foil.
S125: rinsed by Copper Foil dehydrated alcohol, uses cold blowing blower fan to dry up or use filter paper to dry, to prevent Copper Foil oxygen
Change.
S130: utilize graphene oxide dispersion, the electro-deposition being configured to prepare Graphene/metallic composite is molten
Liquid.
Utilize graphene oxide dispersion, the finite concentration graphene oxide solution (pH=7) of configuration, molten in order to strengthen
Liquid electric conductivity, can select NaCl (0.05M) as additional electrolyte.
S140: arrange electrodeposition apparatus parameter, is placed in electrodeposition apparatus by electric depositing solution and metal material, makes after energising
Obtain Graphene/metallic composite.
The configuration mode of electrodeposition apparatus parameter is as shown in the table:
The present invention uses CV (cyclic voltammetric) curved scanning, and voltage range arranges and chooses-1.6～+1.0V ,-1.2V～0V
And-1.4～0V, scanning speed arranges and is chosen for 17mV/s, 10mV/s, 5mV/s, 1mV/s.For 1mg/ml's and 3mg/ml
Graphene oxide, cycle-index arranges and chooses 10～60 (being spaced 5 circulations), for the oxygen of 5mg/ml, 7mg/ml and 11mg/ml
Functionalized graphene cycle-index arranges and is chosen for 1～21 (being spaced 3 circulations).The weight that the present invention uses visually and deposition increases with
The ratio of the contact area of metal material and graphene oxide dispersion solution weighs the quality of deposition effect.
According to electro-deposition basic principle of dynamics, Graphene electro-deposition basic step mainly has a following four step:
1. graphene oxide is by mass transfer near dispersion body electrode surface in opposite directions；
2. graphene oxide adsorbs at electrode surface；
3. graphene oxide and electrode generation electron exchange, be reduced to Graphene；
4. Graphene is insoluble in solvent and is deposited on electrode surface.
In electrochemical deposition process, Graphene is the piecemeal surface being deposited on Copper Foil, just as fallen leaves are mixed and disorderly
Paving is spilt on the ground, due to intermolecular interaction force, unordered arrangement weave in.Owing to electro-deposition occurs at aqueous solution
In, between the graphene layer of deposition unavoidable doping electrolyte from and hydrone, after having deposited, the Graphene of metal surface is darkly
Color spongy (being entrained with more water), the most tightly packed as dried Graphene not image-stone ink.
When electric depositing solution is the graphene oxide solution containing 0.05mol/l NaCl, potential range-1.4～0V, sweep
Retouching speed 5mV/s, when the deposition number of turns is 5, cyclic voltammetry curve such as Fig. 3 institute of Graphene is prepared in graphene oxide electro-deposition
Show.In this cyclic voltammetry curve, it is the peak that graphene oxide is reduced into Graphene, i.e. Graphene at a peak of about about 1.2V
Deposition peak (not up to during this reduction potential, Graphene deposits hardly).B and the c peak of about 0.5V～0V is a pair
Reversible oxidoreduction peak, represents the peak of the oxy radical not being reduced, and this peak is the phenolic hydroxyl group peak on Graphene, and electrification is described
The Graphene reduction learning reduction preparation is the most thorough.Oxidation or reduction current increase with the deposition number of turns and present becoming of incrementally increasing
Gesture, according to peak current density formula, on the premise of not changing electrodeposit liquid, sweep speed and electrochemical reaction, electrode
Surface area become the main cause of curent change.Because Graphene deposits, the surface area of electrode is caused to incrementally increase,
Again because graphene conductive is good, so electric current is increase tendency.
Being different from prior art, the preparation method of the Graphene/metallic composite of the present invention makes oxidized graphite into oxygen
Functionalized graphene dispersion, is configured to electric depositing solution, is together positioned over electricity with electric depositing solution heavy after being cleaned by metal material
In long-pending equipment, set energising reaction after the parameter of electrodeposition apparatus, prepare the Graphene/metal for electronic equipment dissipating heat multiple
Condensation material, can realize the control of Graphene deposit thickness by changing electrochemical parameter, can be by changing metal material
Apparent condition realizes oriented growth Graphene, can realize the control of deposited graphite alkene quality by changing solution concentration.Pass through
The present invention, it is possible to by experimental provision easy, that easily build efficiently, environmental protection prepared have high heat dispersion, non-oxidizability and
Graphene/metallic composite that hydrophobicity is good.
Present invention also offers the embodiment of a kind of Graphene/metallic composite.In the present invention, configuration adds electrolysis
The graphene solution of matter, as electric depositing solution, carries out electro-deposition to metal material in electrodeposition apparatus, finally gives graphite
Alkene/metallic composite.The metal material of conduction processes through certain surface and the inventive method all can be used to realize and graphite
Being combined of alkene, wherein, the Graphene/metallic composite using very thin metal forming to prepare is flexible material, can be made
It is made flexible heat sink device, is expected to apply in wearable electronic field.
According to the heat transfer theory of solid, in solid, there are Electron Heat Conduction and two kinds of heat-conducting modes of lattice conduction of heat.Stone
Ink alkene have complexity dispersion relation, the phonon spectrum of Graphene exists optics ripple simultaneously and acoustics wavelength-division is propped up, and this two
Planting ripple and the most all have compressional wave and shear wave branch, the phonon that optics ripple is corresponding simultaneously, its group velocity is the least, leads thus for lattice
The contribution of heat is the most little, but acoustic wave has the highest energy, and the contribution for specific heat is relatively large.Therefore sound is generally believed
Learning wave sound is heat-carrying particle main in Graphene conduction process, thus Graphene has the heat conductivility of excellence, and matrix
The heat conduction of metallic copper is mainly by the transmission of free electron, therefore in the Graphene Cu-base composites of the present invention, Graphene bag
Cover matrix and improve the heat conductivity of composite.
Being different from prior art, the Graphene/metallic composite of the present invention is to make oxidized graphite into graphene oxide
Dispersion, is configured to electric depositing solution, is together positioned in electrodeposition apparatus with electric depositing solution after being cleaned by metal material,
Set energising reaction after the parameter of electrodeposition apparatus, prepare the Graphene/metallic composite for electronic equipment dissipating heat, can
To realize the control of Graphene deposit thickness by changing electrochemical parameter, can be real by changing the apparent condition of metal material
Existing oriented growth Graphene, can realize the control of deposited graphite alkene quality by changing solution concentration.By means of the invention it is possible to
Efficiently, the prepared of environmental protection has Graphene/metallic composite that high heat dispersion, non-oxidizability and hydrophobicity are good.
The foregoing is only embodiments of the present invention, not thereby limit the scope of the claims of the present invention, every utilization is originally
Equivalent structure or equivalence flow process that description of the invention and accompanying drawing content are made convert, or are directly or indirectly used in what other were correlated with
Technical field, is the most in like manner included in the scope of patent protection of the present invention.
Claims (10)
1. the preparation method of Graphene/metallic composite, it is characterised in that including:
Obtain graphite oxide, utilize described graphite oxide to prepare graphene oxide dispersion；
Obtain metal material, and described metal material is cleaned；
Utilizing described graphene oxide dispersion, the electro-deposition being configured to prepare described Graphene/metallic composite is molten
Liquid；
Electrodeposition apparatus parameter is set, described electric depositing solution and described metal material are placed in described electrodeposition apparatus, energising
Rear prepared described Graphene/metallic composite.
The preparation method of Graphene/metallic composite the most according to claim 1, it is characterised in that in preparation oxidation
In the step of graphite, including step:
Prepared by described graphite oxide material pre-oxidize, neutralized obtaining after drying pre-oxidizes graphite；Wherein, described oxygen
The material of preparing of graphite at least includes: potassium peroxydisulfate, phosphorus pentoxide and natural flake graphite, and mass ratio is 1:1:2；
In described pre-oxidation graphite, add concentrated sulphuric acid, keep low temperature to be also slowly added to potassium permanganate, temperature maintain 10 DEG C with
Under carry out insulation reaction；The mass ratio of described pre-oxidation graphite and described potassium permanganate is 1:3；
Slowly heat up, make temperature step up 35 DEG C with design temperature difference, and it is anti-to maintain temperature to carry out secondary insulation at 35 DEG C
Should；
Add deionized water, 4 seconds one, temperature is maintained at less than 95 DEG C and reacts；Wherein said deionized water and described
The volume ratio of concentrated sulphuric acid is 2:1；
Reaction solution is poured in the mixed solution of deionized water and hydrogen peroxide, staticly settles, add the dilute hydrochloric acid solution of 10%,
Stirring, foam washing 24h, continuous three times.
The preparation method of Graphene/metallic composite the most according to claim 2, it is characterised in that to described oxygen
The material of preparing of graphite carries out, in the step pre-oxidized, further comprising the steps of:
Quality potassium peroxydisulfate and the phosphorus pentoxide such as weigh, add in conical flask, seal with preservative film, measure concentrated sulphuric acid and add cone
In shape bottle, add magneton, put in the water-bath of 80 DEG C and heat, and seal stirring；
Stir and become clarification to solution, continue to add natural flake graphite in described solution, stir, after sealing, put into 80 DEG C
Thermostatic drying chamber, is allowed to react 6 hours；
From described thermostatic drying chamber, take out described conical flask and be cooled to room temperature；
Sample in conical flask carrying out vacuum filtration, is washed with deionized until filtrate is neutrality simultaneously, obtain is described
Pre-oxidation graphite is dried at normal temperatures to constant weight.
The preparation method of Graphene/metallic composite the most according to claim 2, it is characterised in that below 10 DEG C
Carry out in the step of insulation reaction, including step:
In heat-collecting magnetic stirring device, put into mixture of ice and water, be fixedly installed one or three hole flasks, and add a certain amount of the most dry
Dry described pre-oxidation graphite；
In described three hole flasks, add concentrated sulphuric acid, use the stirring paddle of described heat-collecting magnetic stirring device to stir, simultaneously in institute
State and place thermometer in three hole flasks, be maintained at 0 DEG C controlling described three hole pot temperature；
Weighing the potassium permanganate being three times in described pre-oxidation graphite, slowly, be dividedly in some parts described three hole flasks, after adding, insulation is anti-
Answer 2 hours, add ice cube to keep temperature less than 10 DEG C to described water-bath simultaneously.
The preparation method of Graphene/metallic composite the most according to claim 4, it is characterised in that by permanganic acid
Potassium adds in the step of described three hole flasks, and the feed time adding potassium permanganate is half an hour.
The preparation method of Graphene/metallic composite the most according to claim 1, it is characterised in that preparation oxidation stone
The method of ink alkene dispersion is supercentrifugal process or dialysis.
The preparation method of Graphene/metallic composite the most according to claim 1, it is characterised in that to described metal
In the step that material is cleaned, including step:
Preparation deionized water/hydrochloric acid volume ratio is the solution of 1:3, is put into by metal material in described solution, uses ultrasound wave clear
Washing machine ultrasonic cleaning 5min；
Solution is outwelled, and with metal material described in deionized water rinsing；
Add acetone to metal material described in submergence, use described ultrasonic washing unit ultrasonic cleaning 10min, to remove described metal
The oil stain of material surface；
Outwell described acetone, with metal material described in deionized water rinsing；
Described metal material dehydrated alcohol is rinsed, uses cold blowing blower fan to dry up or use filter paper to dry, to prevent described gold
Belong to material oxidation.
The preparation method of Graphene/metallic composite the most according to claim 1, it is characterised in that described in configuration
In the step of electric depositing solution, configure certain density described graphene oxide solution, and add NaCl as additional electrolyte；
Wherein, described graphene oxide solution is neutrality.
The preparation method of Graphene/metallic composite the most according to claim 1, it is characterised in that heavy arranging electricity
In the step of long-pending device parameter, the parameter of described electrodeposition apparatus is arranged such as following table:
10. Graphene/metallic composite, it is characterised in that described Graphene/metallic composite is to be wanted by right
The preparation method seeking the Graphene/metallic composite described in 1-9 prepares.
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