CN102764724A - Method for spraying graphene coat, and graphene coat prepared by same - Google Patents
Method for spraying graphene coat, and graphene coat prepared by same Download PDFInfo
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- CN102764724A CN102764724A CN2012102542000A CN201210254200A CN102764724A CN 102764724 A CN102764724 A CN 102764724A CN 2012102542000 A CN2012102542000 A CN 2012102542000A CN 201210254200 A CN201210254200 A CN 201210254200A CN 102764724 A CN102764724 A CN 102764724A
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Abstract
The invention provides a method for spraying graphene, and a graphene coat prepared by the method. The method comprises the following steps: (1) processing graphite in a microwave oven, then arranging the graphite into a solvent so as to prepare graphene solution; (2) spraying the graphene solution on the surface of a preheated substrate material by a nozzle of a spraying apparatus; and (3) further heating the substrate material optionally. The method of the invention is suitable for preparing graphene radiation coat on the surface of materials, the continuous spraying is realized, the preparation parameters are controlled accurately, the controllable coat material is prepared on the surfaces of materials. The obtained coat is capable of enhancing the radiation property of the surface of materials so as to ensure the high-power output of electronic devices, so that great advantages are provided. Therefore, the method is suitable for the field of radiation technology. With the adoption of the method, the large-scale production of nano graphene chips is realized and the graphene radiation coat with high quality is prepared with low production cost.
Description
Technical field
The invention belongs to new material preparation and sufacing field, relate to a kind of method of Graphene coating and Graphene coating that makes thus of preparing.
Background technology:At present, the electronic device volume is more and more littler, power is increasing, has brought the limitation in dissipation from electronic devices space; Simultaneously, the diversity of material therefor makes that also to prepare the difficulty of thermal interfacial material in surfaces of various materials increasing.How making heat sink material save the space, simultaneously, improve radiating efficiency, is a great problem in current heat radiation field.
Thermal interface material applications is the important component part that constitutes the heat radiation system between thermal source and radiator.The hole that thermal interfacial material produced in the time of can filling up two kinds of different materials of thermal source and radiator and contact prevents heat spot, reduces the impedance that heat is transmitted, and improves thermal diffusivity.The heat-transfer capability of thermal interfacial material is by its atomic structure decision, and the change of crystal structure can influence the thermal heat transfer capability of thermal interfacial material on the nanoscale.Graphene is as a kind of emerging two-dimentional material with carbon element; With its excellent physical chemistry; Be expected to obtain extensive use, be considered to the most promising a kind of material of applying electronic equipment of future generation in fields such as high-performance nano electronic device, composite, field emmision material, gas sensor, energy storages.How to utilize the graphene film of a large amount of nanoscales, lower cost with press close under the industrial processes, be prepared into high-quality thermal interfacial material, be one of significant challenge that faces at present.
Preparation method of graphene has a lot, and chemical vapour deposition technique (CVD) can be prepared high-quality single-layer graphene film in metal substrate surface, after shifting, is applied on the target substrate, is one of important method that realizes graphene-based nano electron device scale.Yet for the application of block materials in the heat dissipation technology field, the graphene film of CVD method preparation is difficult to satisfy the requirement that extensive material uses.
Summary of the invention:The invention provides a kind of method of graphite spraying ene coatings, comprising:
(1) Graphene is added preparation Graphene solution in the solvent;
(2) with the Graphene solution spraying at the substrate material surface of preheating;
(3) optional base material is further heated.
In addition, the Graphene coating that the present invention also provides a kind of spraying to make, its thickness is 0.1-100 μ m, is preferably 1-80 μ m, more preferably 2-60 μ m most preferably is 3-50 μ m.
Method of the present invention is used in material surface and prepares Graphene heat radiation coating, can realize continuous spraying, accurately controls preparation parameter, can prepare the controllable coatings material at material surface.The thermal conductivity of the coating that is obtained is up to 20 W/ (mK); Can improve the heat-sinking capability of material surface to a great extent with respect to business-like heat-conducting glue or heat-conducting silicone grease (thermal conductivity 1～5 W/ (mK)); Thereby guarantee the high power output of electronic device, demonstrate great advantage.Therefore, method of the present invention can be applicable to the heat dissipation technology field.
Can the accomplish scale production graphene film of nanoscale of method of the present invention, production cost is lower, prepares high-quality Graphene heat radiation coating.
Description of drawings:
Fig. 1 is the sketch map of the inventive method of the continuous graphite spraying ene coatings of realization.
The specific embodiment:Embodiment below in conjunction with concrete is described further the present invention, and concrete steps are following:
The method of graphite spraying ene coatings provided by the invention comprises:
(1) Graphene is added preparation Graphene solution in the solvent;
(2) with the Graphene solution spraying at the substrate material surface of preheating;
(3) optional base material is further heated.
In a specific embodiments, base material preheat temperature scope can be 50-250 ℃, preferred 80-200 ℃, more preferably 100-150 ℃, most preferably is 110-140 ℃.
In a specific embodiments, the concentration of said Graphene solution can be 0.05-5 mg/ml, is preferably 0.08-3 mg/ml, and more preferably 0.1-1 mg/ml most preferably is 0.2-0.8 mg/ml.
In step of the present invention (1), said Graphene can be single-layer graphene, multi-layer graphene or its mixture.Wherein, Said single-layer graphene be meant mono-layer graphite atom that molecular skeleton is arranged by hexagonal lattice forms and pass through functionalized and obtain contain the two dimensional surface material that enriches organo-functional group (the organo-functional group molar percentage is generally 5%-30%); Its thickness distribution is between 0.34-1.4 nm, and average diameter is between 10-20 μ m; Said multi-layer graphene is the Graphene of 2-5 layer, and its thickness is between the 0.7-7 nm, and average diameter is between 10-20 μ m.
The Graphene that the present invention uses can adopt method preparations such as mechanical stripping method, epitaxial growth method, epitaxy method and chemical method.Wherein, the mechanical stripping method is the method that goes out graphene film through mechanical force from the sur-face peeling of body phase graphite crystal; Epitaxial growth method is to remove Si through heating monocrystalline 6H-SiC, on monocrystal SiC (001) face, decomposites the Graphene lamella; The epitaxy method is to utilize the atomic structure of growth substrate " kind " to go out Graphene; Chemical method is that graphite oxidation is become graphite oxide; Under ultrasound condition, obtain graphite oxide solution again; Again its reduction is prepared Graphene; The method of reducing of graphite oxide has a lot, (graphite oxide is heated under the atmosphere that inert gas shielding is arranged, make it become black by pale brown look comprising the thermal shock reducing process; Thereby prepare graphene powder) and microwave irradiation (thereby the reduction graphite oxide prepares Graphene in very short time at room temperature), preferably use microwave irradiation that graphite oxide is reduced.
In a specific embodiments; Used Graphene can be the Graphene that is obtained through microwave treatment by expanded graphite, and wherein the granularity (particle diameter) of preferred expanded graphite is more preferably less than 25 μ m less than 30 μ m; Especially preferably less than 20 μ m, most preferably less than 15 μ m; And the power of preferred microwave treatment is the 200-800W/g Graphene, preferred 300-700W/g Graphene, more preferably 400-600W/g Graphene; Most preferably be the 450-550W/g Graphene, the time of microwave treatment is 1-10min, preferred 1-8min; More preferably 1-6min most preferably is 1-5min.
In a specific embodiments; Said solvent is a water; Or organic solvent; For example methyl alcohol, ethanol, isopropyl alcohol, acetone, ethyl acetate, chloroform, carbon tetrachloride, oxolane, N, dinethylformamide, dimethyl sulfoxide (DMSO), benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes; Be preferably water, methyl alcohol, ethanol, acetone, ethyl acetate, chloroform, oxolane, benzene or toluene; More preferably water, methyl alcohol, acetone, ethyl acetate or chloroform; Most preferably be water, chloroform or acetone; Perhaps its mixture.
In a specific embodiments, in Graphene formulations prepared from solutions process, Graphene can adopt the high-energy ultrasonic method to pulverize in solvent; Wherein the frequency of high-energy ultrasonic pulverization process can be 10-30kHz, preferred 12-28kHz, more preferably 15-25kHz; Most preferably be 20-24kHz, output power range can be 100-1000 w/g Graphene, preferred 200-900 w/g Graphene; More preferably 250-750 w/g Graphene most preferably is 300-600 w/g Graphene, and the processing time can be 0.1-48 h; Be preferably 2-36 h, more preferably 5-24 h most preferably is 8-20 h; The Graphene solution that preferably after pulverizing, obtains also can carry out centrifugal treating, and wherein the time range of centrifugal treating can be 5-120 min, is preferably 8-100 min; 10-60 min more preferably; Most preferably be 20-40min, and the range of speeds can be 1000-15000 rpm, be preferably 2000-10000 rpm; More preferably 3000-8000 rpm most preferably is 4000-7000 rpm.
In step of the present invention (2); Wherein, Said base material can be copper, gold, silver, lead, tin, iron, magnesium, plastics (for example polyethylene, polyvinyl alcohol, polypropylene, polystyrene, polyester, polyvinyl chloride, polymethyl methacrylate or polyvinylidene chloride), glass, aluminium, aluminium oxide, pottery (for example aluminium oxide ceramics), PCB (Printed Circuit Board) plate, steel (for example stainless steel, carbon steel), carbon fibre material (for example carbon fiber wire, carbon cloth, carbon fiber tubing), rubber, zinc, alumin(i)um zinc alloy, paper, timber, PWB (Printed wire board) (the layering composite construction that FR-4 and copper are formed), silica, silicon, or its mixture; Preferably copper, lead, tin, iron, plastics, pottery, steel, carbon fibre material, rubber, silica, or its mixture; More preferably copper, lead, plastics, steel, carbon fibre material, or its mixture; Most preferably be copper, plastics, carbon fibre material, or its mixture.
Among the present invention, spraying equipment can be any spraying known in the art or spraying plating equipment, and is unrestricted; But be preferably pneumatic spraying equipment, for example can be available from the H100-D of U.S. PaascheAirbrush company; Voltage static spraying plating equipment for example can be available from the ESR200R2H of Korea S NANONC company; Can be available from the NaBond Electrospinning electrostatic spinning machine of Shenzhen concerted effort micro-nano company; Can be available from the DT-200 type electrostatic spinning machine of the logical development in science and technology Co., Ltd of Dalian ancient cooking vessel etc.More preferably pneumatic spraying equipment wherein.
Among the present invention, the temperature that spraying equipment sprays Graphene solution does not receive any restriction, and its scope can be preferably 0-100 ℃, more preferably environment temperature.
In a specific embodiments, the nozzle of used spraying equipment and substrate material surface distance can be 0.5-10 cm, are preferably 0.8-8 cm, and more preferably 1-5 cm most preferably is 2-4 cm.
In a specific embodiments, the nozzle diameter scope of preferred spraying equipment is 0.05-10 mm, is preferably 0.1-5 mm, and more preferably 0.1-2 mm most preferably is 0.1-0.5 mm.
In a specific embodiments, the spray time scope can be 0.5-10 min, is preferably 0.8-8min, and more preferably 1-5 min most preferably is 2-4 min.
In a specific embodiments, said spraying can be spraying at any angle, is preferably at any angle spraying continuously, and the spraying continuously at any angle of circulation more preferably is until desired thickness.
In step of the present invention (3), the temperature of preheating is identical or different in the temperature of said base material heating and the step (2), and its scope can be 50-250 ℃, preferred 80-200 ℃, more preferably 100-150 ℃, most preferably is 110-140 ℃.
By the Graphene coating of the inventive method preparation, its thickness is 0.1-100 μ m, is preferably 1-80 μ m, and more preferably 2-60 μ m most preferably is 3-50 μ m.
In addition, the Graphene coating that the present invention also provides a kind of spraying to make, its thickness is 0.1-100 μ m, is preferably 1-80 μ m, more preferably 2-60 μ m most preferably is 3-50 μ m.
Method of the present invention is used in material surface and prepares Graphene heat radiation coating, can realize continuous spraying, accurately controls preparation parameter, can prepare the controllable coatings material at material surface.The thermal conductivity of the coating that is obtained is up to 20 W/ (mK); Can improve the heat-sinking capability of material surface to a great extent with respect to business-like heat-conducting glue or heat-conducting silicone grease (thermal conductivity 1～5 W/ (mK)); Thereby guarantee the high power output of electronic device, demonstrate great advantage.Therefore, method of the present invention can be applicable to the heat dissipation technology field.
For understanding the present invention better, hereinafter will combine embodiment to describe the present invention, but will be appreciated that these embodiment are merely the present invention carried out example description, and unrestricted the present invention.
Compound that uses in following examples or reagent are commercially available to be got, and perhaps can known by one of skill in the art conventional method prepare; Employed laboratory apparatus can be buied through commercial sources.
Embodiment
Embodiment 1:The preparation of mono-layer graphite aqueous solution
With 1 g single-layer graphene (according to method described in the one Chinese patent application 200910067708.8 preparation) in 1 L water with the high-energy ultrasonic appearance (available from Shanghai than bright Instr Ltd.; The BILON92-II) condition is handled respectively in the employing table 1, obtains Graphene solution.
Table 1: high-energy ultrasonic condition
| Numbering | 1 | 2 | 3 | 4 | 5 |
| Frequency (kHz) | 20 | 25 | 15 | 23 | 25 |
| Power (W) | 200 | 400 | 600 | 800 | 1000 |
| Time (min) | 60 | 40 | 30 | 20 | 6 |
Embodiment 2:The preparation of single-layer graphene organic solution
With 1 g single-layer graphene (according to method described in the one Chinese patent application 200910067708.8 preparation) at 2 L DMF (N; Dinethylformamide) in the high-energy ultrasonic appearance (available from Shanghai than bright Instr Ltd.; The BILON92-II) condition is handled respectively in the employing table 2, obtains Graphene solution.
Table 2: high-energy ultrasonic condition
| Numbering | 1 | 2 | 3 | 4 | 5 |
| Frequency (kHz) | 20 | 25 | 15 | 23 | 25 |
| Power (W) | 200 | 400 | 600 | 800 | 1000 |
| Time (min) | 60 | 40 | 20 | 10 | 6 |
Embodiment 3:The preparation of the multilayer graphite aqueous solution
With 1 g multi-layer graphene (according to Carbon; 2004; 42; Method described in 2929 preparation) in 3 L water, handles respectively, obtain Graphene solution (the Graphene number of plies is the 2-5 layer) with condition in high-energy ultrasonic appearance (available from Shanghai than bright Instr Ltd., BILON92-II) the employing table 3.
Table 3: high-energy ultrasonic condition
| Numbering | 1 | 2 | 3 | 4 | 5 |
| Frequency (kHz) | 20 | 25 | 15 | 23 | 25 |
| Power (W) | 200 | 400 | 600 | 800 | 1000 |
| Time (min) | 60 | 40 | 20 | 10 | 6 |
Embodiment 4:The preparation of multilayer graphite acetone soln
With 1 g multi-layer graphene (according to Carbon; 2004; 42; Method described in 2929 preparation) in 1 L acetone, handles respectively, obtain Graphene solution (the Graphene number of plies is the 2-5 layer) with condition in high-energy ultrasonic appearance (available from Shanghai than bright Instr Ltd., BILON92-II) the employing table 4.
Table 4: high-energy ultrasonic condition
| Numbering | 1 | 2 | 3 | 4 | 5 |
| Frequency (kHz) | 20 | 25 | 15 | 23 | 25 |
| Power (W) | 200 | 400 | 600 | 800 | 1000 |
| Time (min) | 60 | 40 | 30 | 20 | 6 |
Embodiment 5:With the expanded graphite is the preparation of the graphene aqueous solution of raw material
With 1 g expanded graphite (available from Yan Xin graphite company; High-purity expansible graphite, 32 orders) put into the Power Processing 3min of micro-wave oven with 800W, put into then 10 L water with the high-energy ultrasonic appearance (available from Shanghai than bright Instr Ltd.; The BILON92-II) condition is pulverized respectively in the employing table 5; (available from Beijing industrial Science and Technology Ltd. of auspicious nation, TDL-40B) condition is handled respectively in the employing table 6, obtains Graphene solution (the Graphene number of plies is the 2-5 layer) to use centrifuge again.
Table 5: high-energy ultrasonic condition
| Numbering | 1 | 2 | 3 | 4 | 5 |
| Frequency (kHz) | 20 | 25 | 15 | 23 | 25 |
| Power (W) | 200 | 400 | 600 | 800 | 1000 |
| Time (h) | 24 | 12 | 8 | 5 | 3 |
Table 6: centrifugal treating condition
| Numbering | 1 | 2 | 3 | 4 | 5 |
| Rotating speed (rpm) | 2000 | 4000 | 7000 | 10000 | 13000 |
| Time (min) | 60 | 40 | 20 | 10 | 6 |
Embodiment 6:With the expanded graphite is the preparation of the Graphene acetone soln of raw material
With 1 g expanded graphite (available from Yan Xin graphite company; High-purity expansible graphite, 30 orders) put into micro-wave oven (power 700W) and handle 5 min, put into then 500 ml acetone with the high-energy ultrasonic appearance (available from Shanghai than bright Instr Ltd.; The BILON92-II) condition is pulverized respectively in the employing table 7; (available from Beijing industrial Science and Technology Ltd. of auspicious nation, TDL-40B) condition is handled respectively in the employing table 8, obtains Graphene solution (the Graphene number of plies is the 2-5 layer) to use centrifuge again.
Table 7: high-energy ultrasonic condition
| Numbering | 1 | 2 | 3 | 4 | 5 |
| Frequency (kHz) | 20 | 25 | 15 | 23 | 25 |
| Power (W) | 200 | 400 | 600 | 800 | 1000 |
| Time (h) | 24 | 12 | 8 | 5 | 3 |
Table 8: centrifugal treating condition
| ? | 1 | 2 | 3 | 4 | 5 |
| Rotating speed (rpm) | 2000 | 4000 | 7000 | 10000 | 13000 |
| Time (min) | 60 | 40 | 20 | 10 | 6 |
Embodiment 7:The Graphene solution spraying is prepared the Graphene coating at material surface
The numbering 3 Graphene solution that embodiment 1 is made are injected into spraying equipment (available from U.S. PaascheAirbrush company; Model H100-D) in; The distance of regulating nozzle (diameter is 0.2 mm, shown in 1 among Fig. 1) and copper base material (shown in 2 among Fig. 1) surface is 5 cm, and base material is carried out preheating, and to make its temperature be 100 ℃; Spray 3 min, drying; Wherein base material place driving-belt (as Fig. 13 shown in) go up realizing continuous spraying, thereby preparation Graphene coating, its thickness is 0.9 μ m.Recording its thermal conductivity is 17 W/ (mK) (anti-Shanghai representative office of the instrument Manufacturing Co., Ltd test of speeding of Germany, instrument models: laser method conductometer HFM).
Embodiment 8:The Graphene solution spraying is prepared the Graphene coating at material surface
The numbering 4 Graphene solution that embodiment 2 is made are injected into spraying equipment (U.S. PaascheAirbrush company; Model H100-D) in, the distance of regulating nozzle (diameter is 0.3 mm, shown in 1 among Fig. 1) and aluminium oxide ceramics base material surface is 3 cm and base material is carried out preheating to make temperature be 110 ℃; Spray 2 min; Afterwards this base material being continued to be heated to temperature is 120 ℃, drying, thus preparation Graphene coating, and its thickness is 1 μ m.Recording its thermal conductivity is 18 W/ (mK).(anti-Shanghai representative office of the instrument Manufacturing Co., Ltd test of speeding of Germany, instrument model: laser method conductometer HFM).
Embodiment 9:The Graphene solution spraying is prepared the Graphene coating at material surface
The numbering 2 Graphene solution that embodiment 5 is made are injected into spraying equipment (available from U.S. PaascheAirbrush company; Model H100-D) in; (diameter is 0.4 mm to regulate nozzle; Shown in 1 among Fig. 1) be 2 cm and base material carried out preheating to make its temperature be 120 ℃ with the distance on polyvinyl chloride base material (shown in 3 among Fig. 1) surface, spray 10 min, drying, base material place driving-belt (as Fig. 13 shown in) go up to realize continuous spraying; Thereby preparation Graphene coating, its thickness is 50 μ m.Recording its thermal conductivity is 19 W/ (mK).(anti-Shanghai representative office of the instrument Manufacturing Co., Ltd test of speeding of Germany, instrument model: laser method conductometer HFM).
Embodiment 10:The Graphene solution spraying is prepared the Graphene coating at material surface
The numbering 3 Graphene solution that embodiment 6 is made are injected into spraying equipment (available from U.S. PaascheAirbrush company; Model H100-D) in, the distance of regulating nozzle (diameter is 0.2 mm, shown in 1 among Fig. 1) and stainless steel substrate material surface is 1 cm and base material is carried out preheating to make its temperature be 150 ℃; Spray 5 min; Afterwards this base material is continued to be heated to 150 ℃, drying, thus preparation Graphene coating, and its thickness is 6.25 μ m.Record its thermal conductivity and be respectively 20 W/ (mK).(anti-Shanghai representative office of the instrument Manufacturing Co., Ltd test of speeding of Germany, instrument model: laser method conductometer HFM).
Claims (10)
1. the method for a graphite spraying ene coatings comprises:
(1) Graphene is added preparation Graphene solution in the solvent;
(2) with the Graphene solution spraying at the substrate material surface of preheating;
(3) optional base material is further heated.
2. the process of claim 1 wherein that said base material preheat temperature scope can be 50-250 ℃, preferred 80-200 ℃, more preferably 100-150 ℃, most preferably be 110-140 ℃; And/or in temperature and the step (2) of the heating of base material described in the step (3) temperature of preheating identical or different, its scope can be 50-250 ℃, preferably 80-200 ℃, more preferably 100-150 ℃, most preferably is 110-140 ℃.
3. claim 1 or 2 method, the concentration of wherein said Graphene solution can be 0.05-5 mg/ml, is preferably 0.08-3 mg/ml, more preferably 0.1-1 mg/ml most preferably is 0.2-0.8 mg/ml.
4. claim 1 or 2 method; Wherein said Graphene is expanded graphite, single-layer graphene, multi-layer graphene or its mixture through microwave treatment, and wherein the granularity of preferred expanded graphite is more preferably less than 25 μ m less than 30 μ m; Especially preferably less than 20 μ m, most preferably less than 15 μ m; And the power of preferred microwave is the 200-800W/g Graphene; Preferred 300-700W/g Graphene, more preferably the 400-600W/g Graphene most preferably is the 450-550W/g Graphene; The processing time of microwave treatment is 1-10 min; Preferred 1-8 min, more preferably 1-6 min most preferably is 1-5 min.
5. claim 1 or 2 method; Wherein said solvent is a water; Or organic solvent; For example methyl alcohol, ethanol, isopropyl alcohol, acetone, ethyl acetate, chloroform, carbon tetrachloride, oxolane, N, dinethylformamide, dimethyl sulfoxide (DMSO), benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes; Be preferably water, methyl alcohol, ethanol, acetone, ethyl acetate, chloroform, oxolane, benzene or toluene; More preferably water, methyl alcohol, acetone, ethyl acetate or chloroform; Most preferably be water, chloroform or acetone; Perhaps its mixture.
6. claim 1 or 2 method; Wherein said Graphene adopts the high-energy ultrasonic method to pulverize in solvent; Wherein the frequency of high-energy ultrasonic pulverization process can be 10-30 kHz, preferred 12-28 kHz, more preferably 15-25 kHz, most preferably be 20-24 kHz; Output power range can be 100-1000 w/g Graphene, preferred 200-900 w/g Graphene, more preferably 250-750 w/g Graphene, most preferably be 300-600 w/g Graphene, and the processing time can be 0.1-48 h, is preferably 2-36 h, more preferably 5-24 h, most preferably be 8-20 h; The Graphene solution that preferably after pulverizing, obtains also can carry out centrifugal treating; Wherein the time range of centrifugal treating can be 5-120 min, be preferably 8-100 min, more preferably 10-60 min, most preferably be 20-40 min, and the range of speeds can be 1000-15000 rpm, is preferably 2000-10000 rpm, more preferably 3000-8000 rpm, most preferably be 4000-7000 rpm.
7. claim 1 or 2 method; Wherein said base material can be copper, gold, silver, lead, tin, iron, magnesium, plastics (for example polyethylene, polyvinyl alcohol, polypropylene, polystyrene, polyester, polyvinyl chloride, polymethyl methacrylate or polyvinylidene chloride), glass, aluminium, aluminium oxide, pottery (for example aluminium oxide ceramics), PCB (Printed Circuit Board) plate, steel (for example stainless steel, carbon steel), carbon fibre material (for example carbon fiber wire, carbon cloth, carbon fiber tubing), rubber, zinc, alumin(i)um zinc alloy, paper, timber, PWB (Printed wire board) (the layering composite construction that FR-4 and copper are formed), silica, silicon, or its mixture; Preferably copper, lead, tin, iron, plastics, pottery, steel, carbon fibre material, rubber, silica, or its mixture; More preferably copper, lead, plastics, steel, carbon fibre material, or its mixture; Most preferably be copper, plastics, carbon fibre material, or its mixture.
8. claim 1 or 2 method, the distance of wherein said substrate material surface and said equipment spraying nozzle is 0.5-10 cm, is preferably 0.8-8 cm, more preferably 1-5 cm most preferably is 2-4 cm; And/or the time range of wherein said spraying is 0.5-10 min, be preferably 0.8-8 min, more preferably 1-5 min most preferably is 2-4 min; And said spraying is spraying at any angle, is preferably at any angle spraying continuously, the spraying continuously at any angle of circulation more preferably.
9. claim 1 or 2 method, wherein said Graphene coating layer thickness is 0.1-100 μ m, is preferably 1-80 μ m, more preferably 2-60 μ m most preferably is 3-50 μ m.
10. Graphene coating by each method preparation in the claim 1 to 9, its thickness is 0.1-100 μ m, is preferably 1-80 μ m, more preferably 2-60 μ m most preferably is 3-50 μ m.
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