CN106978606A - A kind of high heat conduction graphene/titanium composite material and preparation method thereof - Google Patents
A kind of high heat conduction graphene/titanium composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106978606A CN106978606A CN201611075214.0A CN201611075214A CN106978606A CN 106978606 A CN106978606 A CN 106978606A CN 201611075214 A CN201611075214 A CN 201611075214A CN 106978606 A CN106978606 A CN 106978606A
- Authority
- CN
- China
- Prior art keywords
- graphene
- titanium
- composite material
- film
- steps
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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)
- Battery Electrode And Active Subsutance (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention provides a kind of preparation method of high heat conduction graphene/titanium composite material, prepares graphene film in titanium or titanium alloy-based plate surface by Process of Electrochemical Reduction, forms graphene/titanium composite material.The preparation method of the present invention is simple, reliable, strong operability, and without using chemical reducing agent, reduces the pollution of chemicals, and reduction and the step of film forming procedure one are completed, and prepared graphene film is fine and close, uniform, thickness is controllable.The thermal conductivity for graphene/titanium composite material that profit is prepared in this way is significantly improved, and can further improve the application of titanium or titanium alloy.
Description
Technical field
The present invention relates to field of compound material, more particularly to a kind of high heat conduction graphene/titanium composite material and its preparation side
Method.
Background technology
Titanium and titanium alloy are widely used in boat because it has the advantages that high intensity, low-density and corrosion resistance and good
My god, aviation, the field such as automobile.But the heat conductivility of titanium and titanium alloy is poor, its room temperature thermal conductivity only has 5-21W/ (mK),
It greatly limit its application.If the thermal conductivity of titanium and titanium alloy can be improved, its application can be wider.
Graphene is the new two-dimensional material of a class, because the performance such as its excellent power, heat, light, electricity, and wide concerned.
The theoretical thermal conductivity of graphene is 3000-5000W/ (mK), and Experimental report value is more than 1000W/ (mK), and heat conductivility is very
It is excellent.There are all kinds of researchs, graphene has been combined with macromolecule, metal and ceramic matrix, improved the heat conductivility of matrix.
2010, graphene was added to indium and indium-gallium system by the report such as K. Jagannadham, and the thermal conductivity of compound rear system is carried
It is high 2-3 times（K. Jagannadham, Journal of Electronic Materials, 2010, 40, 25-34）.
2014, P. Goli etc. grew graphene in copper foil surface, and the thermal conductivity of copper foil improves 24% after being combined（P. Goli, H.
Ning, X. Li, C. Y. Lu, K. S. Novoselov and A. A. Balandin, Nano Letters,
2014, 14, 1497-1503）.
To improve the thermal conductivity of titanium and titanium alloy, graphene is combined by existing scholar with titanium or titanium alloy.For example, 2014
Year, Zheng, H etc. is by magnetron sputtering titanium layer, while in the good graphene of surface dip-coating electronation, repeated multiple times, prepares
Into graphene/titanium composite material, its thermal conductivity brings up to 40W/ (mK) by 21W/ (mK).But this method is complex, stone
The thickness of black thin layer is also difficult to control to（H. Zheng and K. Jaganandham, Journal of Heat Transfer,
2014, 136, 061301-061301）.
The preparation method of graphene has a variety of, including chemical vapour deposition technique, physics stripping method, oxidation-reduction method etc..Its
Middle oxidation-reduction method refers to first prepare graphene oxide, then reduces by chemical reagent or obtain stone by electrochemical reduction
Black alkene.
The present invention directly prepares graphene using the method for electrochemical reduction oxidation graphene in titanium or titanium alloy surface
Film, to improve the thermal conductivity of titanium and titanium alloy.What the method disclosed in the present and all kinds of titanium/graphenes reported were combined
Method has obvious difference.
Such as apply for patent of invention（Application number, 201510125804.9, a kind of graphene/titanium composite material and its preparation side
Method）It is, by ball milling titanium valve and graphene oxide powder, to be then freeze-dried and sinter to prepare graphene/titanium composite material.
Such as apply for patent of invention（Application number 201510685207.1, a kind of graphene enhancing titanium matrix composite and its system
Preparation Method）It is that, by Graphite alkene and titanium valve, after drying, hot pressed sintering obtains graphene enhancing titanium matrix composite.
Such as apply for patent of invention（Application number, 201510341808.0, a kind of preparation method of graphene paper）It is by molten
The method of agent evaporation is first in substrate（Copper sheet, ITO glass or Pt pieces）Upper generation graphene oxide membrane, then using bipolar electrode body
System, using gel as electrolyte, carries out electrochemical reduction in -10V~0V potential ranges, then, soaks, dries, flattens, obtain
Graphene paper.
Such as authorize patent of invention（Authorize publication number, the B of CN 104140096, a kind of preparation method of graphene roll）Be with
Graphene oxide is presoma, and two electrodes are using the smooth copper sheet in surface, and it is 10~30V first to select voltage, carries out positive pole suction
Attached, reconvert voltage direction, selection voltage is 60~80V, carries out cathodic reduction reaction, subsequent pickling, deionized water are clear
Wash, be then sonicated and obtain the graphene roll with curling pleated structure.
Such as authorize patent of invention（Authorize publication number, the B of CN 103208373, Graphene electrodes and preparation method thereof with should
With）It is, using graphene oxide as raw material, but not adjust the pH value of graphene oxide, in the gold of polishing, nickel, aluminium or stainless steel substrate
On, reduced by the constant potential short time（6-50 seconds）, then further reduced in the lithium perchlorate aqueous solution again, through deionized water
After flushing, the three-dimensional porous network structure graphite alkene that aperture is 5-20 microns, thickness is 10-60 microns is obtained, is used as super
The electrode of capacitor etc..Of the invention and above-mentioned patent（Authorize publication number, the B of CN 103208373, Graphene electrodes and its preparation
Method and application）There is obvious difference, show following aspect：（1）Colloidal nature is different with substrate, the B of CN 103208373
Patent does not adjust the pH value of graphene oxide colloid, without electrolyte, uses gold, nickel, aluminium or the stainless steel of polishing for substrate,
And present invention regulation pH value, and addition NaCl or Na2SO4To increase the electric conductivity of system, titanium or titanium alloy are used for base
Plate, the quality of such graphene is higher；（2）Process of Electrochemical Reduction is different, and the B patents of CN 103208373 are short using constant potential
Time（5-60 seconds）Reduction, and the present invention uses continuous electric potential scanning（0~-1.6V）The multi cycle long period reduces, such oxygen
It is more abundant that graphite alkene is reduced；（3）Electrochemical reduction aftertreatment technology is different, and the B patents of CN 103208373 are anti-in electrochemistry
Should after also require that product continues to carry out reduction reaction in lithium perchlorate solution, and the present invention need not；（4）Graphene form is not
Together, the graphite ene product of the B patents of CN 103208373 be loose three-dimensional porous network structure, 10-60 microns of thickness, mainly
Applied to electrode of super capacitor, and graphene prepared by the present invention is fine and close, uniform film-form, 0.4-2.0 microns of thickness,
Predominantly improve the thermal conductivity of substrate.
When preparing titanium/graphene composite material, existing method technique is complex.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of technique is simple, reliable, strong operability, no
Using chemical reducing agent, and graphene film is fine and close, uniform, thickness is controllable, the higher graphene/titanium composite material of thermal conductivity and its
Preparation method.
To achieve the above object, the invention discloses a kind of preparation method of high heat conduction graphene/titanium composite material,
Comprise the following steps：
S101, configures graphene oxide colloid：Graphene oxide colloid is configured, its pH value is adjusted, and to graphene oxide colloid
Middle a certain amount of electrolyte of addition；
S102, electrochemical reduction oxidation graphene：Using the method for electrochemical reduction oxidation graphene, in titanium or titanium alloy substrate
On prepare graphene film；
S103, rinses graphene film：Rinse titanium or the graphene film of titanium alloy-based plate surface；
S104, is dried：At a certain temperature, certain time is dried, that is, obtains graphene/titanium composite material.
Further, in the preparation method of above-mentioned graphene/titanium composite material,
The concentration of the graphene oxide colloid configured in the S101 steps is 7-35mg/mL.
Further, in the preparation method of above-mentioned graphene/titanium composite material,
The pH value of graphene oxide colloid is adjusted using the one or two kinds of of ammoniacal liquor or sodium hydroxide in the S101 steps,
And the pH value after regulation is 6.5-7.
Further, in the preparation method of above-mentioned graphene/titanium composite material,
Electrolyte used is the one or two kinds of of sodium chloride or sodium sulphate in the S101 steps, and it is in graphene oxide
Concentration in colloid is 0.05-0.1 mol/Ls.
Further, in the preparation method of above-mentioned graphene/titanium composite material,
In the S102 steps, using three-electrode system electrochemical workstation carry out electrochemical reduction, working electrode be titanium or
Titanium alloy substrate, is graphite or platinum to electrode, reference electrode is saturated calomel electrode, and three electrodes are all placed in S101 configurations
Graphene oxide colloid in.
Further, in the preparation method of above-mentioned graphene/titanium composite material,
In the S102 steps, during electrochemical reduction, using continuous electric potential scanning, sweep speed is 3-10mV/s, voltage window
For 0~-1.6V, cycle-index is 5-20 times.
Further, in the preparation method of above-mentioned graphene/titanium composite material,
Cleaning agent used is deionized water, the one or two kinds of of absolute ethyl alcohol in the S103 steps.
Further, in the preparation method of above-mentioned graphene/titanium composite material,
Drying in the S104 steps is to spontaneously dry, and drying temperature is 20-40 DEG C, and drying time is 0.5-10 hours.
The invention also discloses a kind of high heat conduction graphene/titanium composite material, it is one of method preparation by mentioned earlier
Obtain, and the graphene forms film like structures fine and close, that uniform, thickness is controllable on the surface of titanium or titanium alloy substrate,
Film thickness is 400 ~ 2000nm；And thermal conductivity of the thermal conductivity than titanium or titanium alloy substrate of the graphene/titanium composite material
Improve 20-80%.
The present invention is prepared fine and close, uniform, thick using electrochemical reduction oxidation graphene technique on titanium or titanium alloy substrate
The controllable graphene film of degree, can significantly improve the thermal conductivity of titanium or titanium alloy substrate：
1）The preparation method of the present invention is simple, reliable, strong operability, and without using chemical reducing agent, passes through electrochemical reduction
Method directly prepares graphene film on titanium or titanium alloy substrate, without being coated with using first electronation, or first coats
The method of electronation, reduction and film forming procedure are combined again, are directly prepared using electrochemical reduction oxidation graphene
Graphene film, reduces the pollution of chemicals；
2）Prepared graphene film is fine and close, uniform and thickness is controllable, can be by the scan cycle number of times of electrochemical reduction
To control the thickness of graphene film, cycle-index is more, and graphene film is thicker；
3）Improved using the thermal conductivity of graphene/titanium composite material prepared by the present invention than the thermal conductivity of titanium or titanium alloy substrate
20-80%。
In a word, method of the invention is simple, reliable, strong operability, without using chemical reducing agent, and graphene film is caused
Close, uniform, thickness is controllable, and the thermal conductivity of graphene/titanium composite material of preparation is more obvious than the thermal conductivity of titanium or titanium alloy substrate
Improve.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing skill
Accompanying drawing required in art description is briefly described.
Fig. 1 is the schematic flow sheet of preparation method disclosed in this invention.
Fig. 2 is the electrochemical reduction device structure schematic diagram with preparation method disclosed in this invention, wherein 21 be work
Electrode, 22 be reference electrode, and 23 be that, to electrode, 24 be electrochemical workstation, and 25 be the graphene oxide colloid configured, and 26 are
Container.
Fig. 3 is the structural representation with graphene/titanium composite material prepared by preparation method disclosed in this invention, figure
3A is three dimensional structure diagram, and Fig. 3 B are section structure schematic diagram, wherein 31 be titanium or titanium alloy substrate, 32 be that graphene is thin
Film.
Fig. 4 is to be shone with graphene/titanium composite material prepared by preparation method disclosed in this invention and titanium-base optics
Piece, Fig. 4 A are the optical photograph of titanium-base, and Fig. 4 B are the optical photograph of prepared graphene/titanium composite material.
Fig. 5 is the scanning electron microscopy with graphene/titanium composite material prepared by preparation method disclosed in this invention
Mirror photo, wherein Fig. 5 A are cross-sectional scanning electron microphotograph, and Fig. 5 B are surface Scanning Electron microphotograph, and 51 be titanium-based
Plate, 52 be graphene film.
Fig. 6 is the partial sweep electronics with graphene/titanium composite material prepared by preparation method disclosed in this invention
Microphotograph, Fig. 6 A are the partial sweep electron micrograph of sample prepared by embodiment 1, and Fig. 6 B are that embodiment 2 is made
The partial sweep electron micrograph of standby sample, 61 be titanium-base, and 62 be graphene film.
Fig. 7 is with the graphene/titanium composite material and the X-ray of Ti substrates prepared by preparation method disclosed in this invention
Diffracting spectrum.
Fig. 8 is with the graphene/titanium composite material and the plane of Ti substrates prepared by preparation method disclosed in this invention
Thermal conductivity compares.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment, but the present invention is not limited to following examples institute
Content is stated, the other embodiments based on inventive concept, also among protection scope of the present invention.
Embodiment 1
1.S101, configure graphene oxide colloid：The graphene oxide powder of certain mass is dissolved in deionized water, configured dense
The graphene oxide colloid for 7mg/mL is spent, addition NaOH regulation colloids pH is 7, and addition NaCl electrolyte to concentration rubs for 0.05
You/liter；
2.S102, electrochemical reduction oxidation graphene：Using the method for electrochemical reduction oxidation graphene, prepared on Ti substrates
Graphene film, using titanium-base as working electrode, using platinum as to electrode, using saturated calomel electrode as reference electrode, and and CHI
760E electrochemical workstations are connected, and above-mentioned three electrode are placed in the graphene oxide colloid that S101 has been configured, using continuous
Electric potential scanning, sweep speed is 3mV/s, and voltage window is 0~-1.6V, and cycle-index is 5 times；
3.S103, rinse graphene film：The graphene film of titanium-based plate surface is successively cleaned using ethanol and deionized water；
4.S104, dry：Spontaneously dried 10 hours at 20 DEG C, just obtain graphene/titanium composite material, be designated as sample 1.
Fig. 2 is the electrochemical reduction device structure schematic diagram with preparation method disclosed in this invention, wherein 21 be work
Electrode, 22 be reference electrode, and 23 be that 24 be electrochemical workstation, according to connection electrode as shown in the figure to electrode.Fig. 3 is with this
The structural representation of graphene/titanium composite material prepared by the disclosed preparation method of invention, Fig. 3 A illustrate for three-dimensional structure
Figure, Fig. 3 B are section structure schematic diagram, wherein 31 be titanium or titanium alloy substrate, 32 be graphene film, i.e., through electrochemical deposition
Afterwards, in the layer graphene film of titanium-base superficial growth one.Fig. 4 is with the graphene/titanium composite material and titanium prepared by embodiment
Substrate optical photograph, Fig. 4 A are the optical photograph of titanium-base, and Fig. 4 B shine for the optics of prepared graphene/titanium composite material
Piece, as seen from the figure, one layer of densification, uniform black graphene film in titanium-base superficial growth.Fig. 5 is that the present embodiment is made
The electron scanning micrograph of standby graphene/titanium composite material, wherein Fig. 5 A are cross-sectional scanning electron microphotograph, figure
5B is surface Scanning Electron microphotograph, and 51 be titanium-base, and 52 be graphene film.From Fig. 5 A, in titanium-based plate surface
Really a layer graphene film is generated.Because the graphene film is transparent under an electron microscope, in order to more obvious
The graphene film is observed, a part of graphene film is removed, Fig. 5 B are the front electronics after part graphene film removes
Growth has graphene film above left-half in microphotograph, Fig. 5 B, and right half part graphene film is removed, boundary
Limit is clearly.Numerous cuts in figure are produced in titanium-base production process.Prepared graphene is in film-form, cause
Close, uniform, thickness is 400-500nm, and non-network cavernous structure.Graphene/titanium composite material prepared by embodiment 1
Room temperature thermal conductivity（21.5W/(m·K)）Than the room temperature thermal conductivity of titanium-base used（17.8W/(m·K)）Lifting ~ 20%.
Embodiment 2
1.S101, configuration graphene oxide colloid, cleaning titanium-base：By the graphene oxide powder of certain mass be dissolved in from
In sub- water, configuration concentration is 7mg/mL graphene oxide colloid, and addition NaOH regulation colloids pH is 7, adds NaCl electrolyte
It is 0.05 mol/L to concentration；
2.S102, electrochemical reduction oxidation graphene：Using the method for electrochemical reduction oxidation graphene, prepared on Ti substrates
Graphene film, using titanium-base as working electrode, using platinum as to electrode, using saturated calomel electrode as reference electrode, and and CHI
760E electrochemical workstations are connected, and above-mentioned three electrode are placed in the graphene oxide colloid that S101 has been configured, using continuous
Electric potential scanning, sweep speed is 3mV/s, and voltage window is 0~-1.6V, and cycle-index is 10 times；
3.S103, rinse graphene film：The graphene film of titanium-based plate surface is successively cleaned using ethanol and deionized water；
4.S104, dry：Spontaneously dried 10 hours at 20 DEG C, just obtain graphene/titanium composite material, be designated as sample 2.
Fig. 6 shines for the partial sweep electron microscope of graphene/titanium composite material prepared by embodiment 1 and embodiment 2
Piece, Fig. 6 A are the partial sweep electron micrograph of graphene/titanium composite material prepared by embodiment 1, and its electrochemistry is also
Former number of times is the circulation of 5 times, i.e., 5, and the thickness of graphene film is 400-500nm, and Fig. 6 B are the graphite prepared by embodiment 2
The partial sweep electron micrograph of alkene/titanium composite material, its electrochemical reduction number of times is 10 times, i.e., 10 circulation, its stone
The thickness of black alkene film is 800-1000nm, wherein 61 be titanium-base, 62 be graphene film.It follows that by controlling electricity
The number of times of electronation, i.e. cycle-index can control the thickness of the graphene film of growth, and cycle-index is more, and graphene is thin
Film is thicker.Fig. 7 is with the graphene/titanium composite material and the X-ray of Ti substrates prepared by preparation method disclosed in this invention
Three lines of upper, middle and lower in diffracting spectrum, figure are the X ray diffracting spectrum of embodiment 2, embodiment 1 and titanium-base, i.e., 10 respectively
Circulate the X ray diffracting spectrum of electrochemical reduction, 5 circulation electrochemical reductions and titanium-base.35.2 °, 38.7 °, 40.4 ° in figure
(100) of titanium are correspond to respectively with the diffraction maximum at 53.3 °, (002), (101) and (102) crystal face (JCPDS 44-
1294).23 ° or so of broad peak（At dashed rectangle）From graphene film（The graphene oxide film of reduction）.Clearly,
Graphene film is generated on the titanium-base of Examples 1 and 2, and the graphene generated is in film-form, densification, uniform, sample
The thickness of the graphene film of product 1 is 400-500nm, and the thickness of the graphene film of sample 2 is 800-1000nm, is fully said
It is bright, can be by the number of times of scan cycle during electrochemical reduction, to control the thickness of graphene film, cycle-index is more, thin
Film is thicker.These graphene films all do not have network cavernous structure.Exactly because present invention employs special electrochemical process,
And graphene oxide colloid is adjusted, it is just unexpected to generate this fine and close, uniform graphene film.This hair
The bright pH value to graphene oxide colloid is adjusted, and adds electrolyte to increase the conduction of graphene oxide colloid
Property, in electrochemical reduction, using continuous voltage scan pattern, multi cycle reduction is carried out, these measures are all conducive to aoxidizing stone
The further reduction of black alkene, facilitates the generation of fine and close, uniform graphene film.Moreover, this fine and close, uniform graphene
Film, determines its excellent heat conductivility.In order to further illustrate the advantage of preparation method disclosed in this invention, Fig. 8 ratios
Compared with the thermal conductivity of prepared graphene/titanium composite material of the invention and Ti substrates.Block diagram in Fig. 8 is respectively embodiment
The plane thermal conductivity of composite prepared by composite, embodiment 2 and titanium-base prepared by 1.As seen from the figure, implementing
The thermal conductivity of composite prepared by example 1 and 2 apparently higher than titanium-base thermal conductivity, and growth graphene film it is thicker
Thermal conductivity is higher, i.e. thermal conductivity of the thermal conductivity of composite prepared by embodiment 2 higher than the composite prepared by embodiment 1
Rate, this is absolutely proved, the graphene film that the present invention is prepared on titanium-base can significantly improve the thermal conductivity of titanium-base.It is real
Apply the room temperature thermal conductivity of graphene/titanium composite material prepared by example 2（24.7W/(m·K)）Than the room temperature heat of titanium-base used
Conductance（17.8W/(m·K)）Lifting ~ 39%.
Embodiment 3
1.S101, configuration graphene oxide colloid, cleaning titanium alloy substrate：The graphene oxide powder of certain mass is dissolved in
In ionized water, configuration concentration is 35mg/mL graphene oxide colloid, and addition ammoniacal liquor regulation colloid pH is 6.5, adds Na2SO4
Electrolyte to concentration is 0.1 mol/L；
2.S102, electrochemical reduction oxidation graphene：Using the method for electrochemical reduction oxidation graphene, in TC4（A kind of titanium is closed
Gold）Graphene film is prepared on substrate, using TC4 substrates as working electrode, using graphite as to electrode, using saturated calomel electrode as ginseng
Connected than electrode, and with CHI 760E electrochemical workstations, above-mentioned three electrode is placed in the graphene oxide that S101 has been configured
In colloid, using continuous electric potential scanning, sweep speed is 10mV/s, and voltage window is 0~-1.6V, and cycle-index is 20 times；
3.S103, rinse graphene film：The graphene film of titanium alloy-based plate surface is cleaned using ethanol；
4.S104, dry：Spontaneously dried 0.5 hour at 40 DEG C, just obtain titanium alloy/graphene film composite.
Clearly, one layer of densification, uniform black thin film are generated in TC4 substrate surfaces, the black thin film is graphite
Alkene film, its thickness is 1800-2000nm.The room temperature thermal conductivity of graphene/titanium composite material prepared by embodiment 3（27.0
W/(m·K)）Than titanium alloy substrate used（TC4）Room temperature thermal conductivity（15.0 W/(m·K)）Lifting 80%.
Claims (9)
1. a kind of preparation method of high heat conduction graphene/titanium composite material, comprises the following steps：
S101, prepares graphene oxide colloid：Graphene oxide colloid is prepared, its pH value is adjusted, and to graphene oxide colloid
Middle a certain amount of electrolyte of addition；
S102, electrochemical reduction oxidation graphene：Using the method for electrochemical reduction oxidation graphene, in titanium or titanium alloy substrate
On prepare graphene film；
S103, rinses graphene film：Rinse titanium or the graphene film of titanium alloy-based plate surface；
S104, is dried：At a certain temperature, certain time is dried, that is, obtains graphene/titanium composite material of high heat conduction.
2. the method as described in claim 1, it is characterised in that
The concentration of the graphene oxide colloid configured in the S101 steps is 7-35mg/mL.
3. the method as described in claim 1, it is characterised in that
The pH value of graphene oxide colloid is adjusted in the S101 steps using the one or two kinds of of ammoniacal liquor, sodium hydroxide, and
PH value after regulation is 6.5-7.
4. the method as described in claim 1, it is characterised in that
Electrolyte used is the one or two kinds of of sodium chloride or sodium sulphate in the S101 steps, and it is in graphene oxide
Concentration in colloid is 0.05-0.1 mol/Ls.
5. the method as described in claim 1, it is characterised in that
In the S102 steps, using three-electrode system electrochemical workstation carry out electrochemical reduction, working electrode be titanium or
Titanium alloy substrate, is graphite or platinum to electrode, reference electrode is saturated calomel electrode, and three electrodes are all placed in S101 configurations
Graphene oxide colloid in.
6. as claim 1-5 any one of method, it is characterised in that
In the S102 steps, during electrochemical reduction, using continuous electric potential scanning, sweep speed is 3-10mV/s, voltage window
For 0~-1.6V, cycle-index is 5-20 times.
7. the method as described in claim 1, it is characterised in that
Irrigation used is deionized water, the one or two kinds of of absolute ethyl alcohol in the S103 steps.
8. the method as described in claim 1, it is characterised in that
Drying in the S104 steps is to spontaneously dry, and drying temperature is 20-40 DEG C, and drying time is 0.5-10 hours.
9. a kind of high heat conduction graphene/titanium composite material, it is characterised in that
Graphene/the titanium composite material is prepared by any one of claim 1-8 method；
The graphene forms film like structures fine and close, that uniform, thickness is controllable on the surface of titanium or titanium alloy substrate, and film is thick
Spend for 400 ~ 2000nm；And the thermal conductivity of prepared graphene/titanium composite material is carried than the thermal conductivity of titanium or titanium alloy substrate
It is high by 20~80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611075214.0A CN106978606B (en) | 2016-11-30 | 2016-11-30 | A kind of high thermal conductivity graphene/titanium composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611075214.0A CN106978606B (en) | 2016-11-30 | 2016-11-30 | A kind of high thermal conductivity graphene/titanium composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106978606A true CN106978606A (en) | 2017-07-25 |
| CN106978606B CN106978606B (en) | 2019-01-01 |
Family
ID=59340942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611075214.0A Active CN106978606B (en) | 2016-11-30 | 2016-11-30 | A kind of high thermal conductivity graphene/titanium composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106978606B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112091219A (en) * | 2019-06-17 | 2020-12-18 | 中国科学院宁波材料技术与工程研究所 | Graphite-titanium composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101634032A (en) * | 2009-08-14 | 2010-01-27 | 南京大学 | Green and fast electrochemical preparation method for graphene |
| KR20140018538A (en) * | 2012-08-02 | 2014-02-13 | 충북대학교 산학협력단 | Method for preparation of the reduced graphene oxide(rgo) by electrochemical reduction |
| CN104947134A (en) * | 2015-07-13 | 2015-09-30 | 湖南农业大学 | Preparation method of porous graphene |
| CN105140497A (en) * | 2015-09-10 | 2015-12-09 | 昆明理工大学 | Application of graphene/copper composite electrode material |
-
2016
- 2016-11-30 CN CN201611075214.0A patent/CN106978606B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101634032A (en) * | 2009-08-14 | 2010-01-27 | 南京大学 | Green and fast electrochemical preparation method for graphene |
| KR20140018538A (en) * | 2012-08-02 | 2014-02-13 | 충북대학교 산학협력단 | Method for preparation of the reduced graphene oxide(rgo) by electrochemical reduction |
| CN104947134A (en) * | 2015-07-13 | 2015-09-30 | 湖南农业大学 | Preparation method of porous graphene |
| CN105140497A (en) * | 2015-09-10 | 2015-12-09 | 昆明理工大学 | Application of graphene/copper composite electrode material |
Non-Patent Citations (1)
| Title |
|---|
| SHAW YONG TOH ET AL.,: ""Graphene production via electrochemical reduction of graphene oxide:Synthesis and characterisation"", 《,CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112091219A (en) * | 2019-06-17 | 2020-12-18 | 中国科学院宁波材料技术与工程研究所 | Graphite-titanium composite material and preparation method and application thereof |
| CN112091219B (en) * | 2019-06-17 | 2022-08-19 | 中国科学院宁波材料技术与工程研究所 | Graphite-titanium composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106978606B (en) | 2019-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107017383B (en) | A kind of three-dimensional porous aluminium foil processing method applied to battery, energy-storage battery plus plate current-collecting body | |
| CN104164690B (en) | Cathode plasma electrolysis extensive deposition coating and the method for surface modification | |
| CN100417749C (en) | Titanium dioxide nano material film and preparation method thereof | |
| CN104269278B (en) | A kind of self-supporting nanoporous nickel nickel compound electric pole piece and preparation method thereof | |
| CN105908220B (en) | A kind of method that liquid electrodeposition prepares micro-nano silver dendrite | |
| CN105734642B (en) | A kind of high-intensitive, the black coating of bigger serface titanium preparation method | |
| CN105088312B (en) | The preparation method of titanium dioxide nano-pipe array thin film | |
| CN104911662A (en) | Preparation method of composite ceramic coating layer | |
| CN102251232A (en) | Method for preparing silver nanowire array in ordered porous alumina template | |
| CN105632790B (en) | A kind of MnO2Nano-array electrode material for super capacitor and preparation method thereof | |
| Liu et al. | The effects of electro-deposition current parameters on performance of tungsten coating | |
| CN106350849A (en) | Method for preparing solar spectrum high-absorption and low-emission oxidation films on aluminum surfaces by means of electro-deposition | |
| Shen et al. | Fabrication of micro/nanoporous templates with a novel hierarchical structure by anodization of a patterned aluminum surface | |
| CN102660765B (en) | Preparation method of porous titanium | |
| CN108950651A (en) | A kind of preparation method of the magnesium alloy surface micro-arc electrophoresis layer of biological composite membrane containing HA | |
| CN111394771A (en) | Method for preparing coating on surface of copper and copper alloy and copper product | |
| CN106978606B (en) | A kind of high thermal conductivity graphene/titanium composite material and preparation method thereof | |
| CN104404565B (en) | Au/TiO2optoelectronic pole of nanotube composite construction and preparation method thereof | |
| CN103290417A (en) | Preparation method of titanium dioxide (TiO2) nanotube film on stainless steel surface | |
| CN108163932A (en) | A kind of PbO of the three-dimensional macroporous structure of doped metal ion2The preparation method of electrode | |
| CN102851720B (en) | A kind of aluminate electrolytic solution and preparing the application in magnesium alloy differential arc oxidation film | |
| CN101498024A (en) | Method for preparing ceramic film on titanium alloy surface | |
| CN106906505A (en) | It is a kind of that the method that ceramic coating improves titanium-base alloy high temperature oxidation resistance is obtained based on halide effect and pretreatment | |
| CN110306199A (en) | A kind of carbon dioxide electro-catalysis reduction film and the preparation method and application thereof | |
| CN107490652B (en) | A kind of construction method of single-orientated yttrium oxide nano-array preparation and membrane electrode |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |