CN109982459A - A kind of graphene composite heating silk and preparation method thereof - Google Patents
A kind of graphene composite heating silk and preparation method thereof Download PDFInfo
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- CN109982459A CN109982459A CN201910274434.3A CN201910274434A CN109982459A CN 109982459 A CN109982459 A CN 109982459A CN 201910274434 A CN201910274434 A CN 201910274434A CN 109982459 A CN109982459 A CN 109982459A
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- heating silk
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/40—Heating elements having the shape of rods or tubes
- H05B3/54—Heating elements having the shape of rods or tubes flexible
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention belongs to exothermic material technical fields, and in particular to a kind of graphene composite heating silk and preparation method thereof.Graphene: (1) being placed in concentrated acid by preparation method, carries out back flow reaction, obtains functionalization graphene；(2) above-mentioned functionalization graphene is dispersed in dispersion liquid, coupling agent is added under stirring condition, obtain the graphene of surface grafting coupling agent；(3) graphene of surface grafting coupling agent and macromolecule resin are added in organic solvent, heating stirring obtains graphene/polymer resin compounded slurry, after being then immersed in carbon fiber 1-3h, carbon fiber is taken out, heating obtains the carbon fiber of surface cure composite mortar；(4) under nitrogen atmosphere, the carbon fiber of surface cure composite mortar is subjected to carbonization treatment, obtains graphene composite heating silk.The present invention is easy to operate, at low cost, is convenient for industrialized production, and obtained graphene composite heating silk heating efficiency is high, low energy consumption.
Description
Technical field
The invention belongs to exothermic material technical fields, and in particular to a kind of graphene composite heating silk and preparation method thereof.
Background technique
Currently, being easy to using carbon-based material as the electric heating material of representative with its high-strength light, electric conversion efficiency height, softness
The significant advantage of knitting forming, as flexible electrothermal membrane, planar heat producing body element, in petroleum pipeline heat preservation, electrothermal heating, snow melt
Change the fields such as ice, health care to be just widely used.
But carbon-based electric heating material still has many deficiencies.For example, carbon crystal electric hotting mask is exactly with carbon particle or short
Carbon fiber is conductive material, and a kind of heating film made of compressed with adhesive is added.This carbon crystal electric hotting mask is easy to aging, and the thermal efficiency declines
Subtract serious, carbon particle and the easy delamination of adhesive, easy release pernicious gas during fever, and there are voltage breakdown electric leakage wind
Danger, service life are shorter.The heating base material of electrothermal carbon fibre membrane is made of long carbon fiber, and its advantages are light, softnesses.But due to
Carbon fiber is usually stretched through charing by macromolecule presoma and is obtained, and belongs to the transition state carbon that organic matter is transformed, microcosmic knot
Structure is similar to graphite, but the arrangement of level and irregular, and belonging to random graphits structure, (carbon i.e. between layers is former not to advise
Fixation position then lacks three-dimensional order, and interlamellar spacing is bigger than graphite crystal).The graphite microcrystal Turbostratic of carbon fiber, it is inevitable
So that it still has a certain distance in terms of electron-transport, heat transfer, thermal stability, and temperature damping is serious, it is difficult to control.
Therefore, developing efficient, the environmentally protective carbon-based exothermic material of high-performance is just becoming the inexorable trend of future development.
Graphene is a kind of Two-dimensional Carbon nanometer material for forming hexangle type in honeycomb lattice with sp2 hybridized orbit by carbon atom
Material.Graphene is to be currently known one kind most thin in material, and quality very rigid transmits electronics under room temperature state
Speed is all faster than known conductor, has excellent thermal conductivity, electric conductivity, mechanical characteristic etc., it is considered to be a kind of future revolution
Property material, these and its extremely special characteristic make it possess incomparable huge development space in exothermic material field.It utilizes
This characteristic of graphene, can make up that current carbon fiber heating material fault of construction is more, heating efficiency is low, temperature damping is serious
Phenomenon.
Summary of the invention
In order to solve the problems, such as that carbon fiber heating material heating efficiency is low in the prior art, the purpose of the present invention is to provide
A kind of heating efficiency is high, low energy consumption, and the graphene composite heating silk and preparation method thereof for being easy to produce in enormous quantities.
The present invention uses concentrated acid to be surface-treated graphene first, functionalization group is introduced, then with coupling agent pair
Graphene surface carries out graft modification.By modified graphene and easily charing macromolecule resin in organic solvent, it is configured to multiple
Slurry is closed, composite mortar is coated in carbon fiber surface, finally by the carbon fiber high temperature under nitrogen protection of composite mortar coating
Charing.The amorphous nanocarbon particle easily formed after the charing of charing macromolecule resin is between graphene and carbon fiber, without fixed
Shape nanocarbon particle can introduce newly-generated C-C chemical bond between graphene sheet layer and carbon fiber substrate, enhance graphene sheet layer
Interaction between carbon fiber substrate improves heating efficiency, reduces energy consumption.
Technical solution of the present invention includes the following:
A kind of graphene composite heating silk, including carbon fiber, graphene and amorphous nanocarbon particle, wherein the graphite
Alkene and amorphous nanocarbon particle are coated on the surface of carbon fiber.
Another object of the present invention, which also resides in, provides a kind of preparation method of graphene composite heating silk, including such as
Lower step:
(1) graphene being placed in concentrated acid, then heating ultrasound carries out back flow reaction, then be diluted, filter, dry,
Obtain functionalization graphene；
(2) above-mentioned functionalization graphene is dispersed in dispersion liquid, obtains graphene solution, heating ultrasound, stirring condition
Lower addition coupling agent, heated under vacuum to dispersion liquid evaporating completely, obtains the graphene of surface grafting coupling agent；
(3) graphene of surface grafting coupling agent and macromolecule resin are added in organic solvent, heating stirring obtains stone
Then black alkene/macromolecule resin composite mortar takes impregnated carbon fiber in the graphene/polymer resin compounded slurry
Carbon fiber out, heating, obtains the carbon fiber of surface cure graphene/polymer resin compounded slurry；
(4) under nitrogen atmosphere, the carbon fiber of above-mentioned surface cure graphene/polymer resin compounded slurry is carbonized
Processing, obtains graphene composite heating silk.
Specifically, the graphene, concentrated acid, dispersion liquid, coupling agent, macromolecule resin, organic solution and carbon fiber, by matter
Amount number is calculated as:
Preferably, the temperature of back flow reaction described in step (1) is 60-80 DEG C, reaction time 2-3h；Step (1)~
The temperature of heating described in step (3) is 40-70 DEG C；The ultrasonic time described in step (1) and step (2) is 1-2h.
Preferably, the time of stirring described in step (2) is 10-12h；The time of stirring described in step (3) is 1-3h,
The time of the dipping is 1-3h；Carbonization treatment described in step (4) is to be placed in tube furnace at 400-600 DEG C to be calcined
2-3h。
Preferably, concentrated acid described in step (1) is the mixture of one or both of the concentrated sulfuric acid and concentrated nitric acid.
Preferably, coupling agent described in step (2) is silane coupling agent, titanate coupling agent, organochromium complexes coupling
One of agent and aluminate coupling agent are a variety of, and the dispersion liquid is distilled water, ethyl alcohol or acetone.
Preferably, the macromolecule resin in step (3) be selected from polystyrene, polycarbonate, polyamide, polyimides and
One or more of polymethyl methacrylate.
Preferably, organic solvent described in step (3) is selected from benzene,toluene,xylene, tetrahydrofuran, acetone, dimethyl methyl
One of amide, ethyl acetate and petroleum ether are a variety of.
Beneficial effects of the present invention:
(1) present invention is first surface-treated graphene using concentrated acid, introduces functionalization group (hydroxyl, carboxyl
Deng), the functionalization group which introduces is very beneficial for grafting of the next step coupling agent to graphene；Another party
The group in face, these functionalization of graphene surface enables graphene to be preferably dispersed in macromolecule resin, avoid by
The heating efficiency of composite heating silk is unevenly influenced in graphene dispersion.
(2) modified graphene and easily charing macromolecule resin are dissolved in organic solvent, are configured to composite mortar, will answer
It closes slurry and is coated in carbon fiber surface, finally by the carbon fiber high temperature carbonization under nitrogen protection of composite mortar coating.Easily charing
The amorphous nanocarbon particle formed after macromolecule resin charing is between graphene and carbon fiber, amorphous nanocarbon particle
Newly-generated C-C chemical bond can be introduced between graphene sheet layer and carbon fiber substrate, enhance graphene sheet layer and carbon fiber substrate
Between interaction.Under electric field action, carbon atom carries out " Brownian movement ", between graphene sheet layer and carbon fiber substrate
Amorphous nanocarbon particle enhances the severe friction generated between carbon atom and shock, improves heating efficiency, reduces energy consumption.
(3) present invention is easy to operate, at low cost, is convenient for industrialized production, obtained graphene composite heating silk heating efficiency
Height, low energy consumption.
Detailed description of the invention
Fig. 1 is the flow diagram that the present invention prepares graphene composite heating silk.
Fig. 2 is that the scanning electron of the graphene composite heating silk (B) prepared in commercialization carbon fiber (A) and embodiment 1 is aobvious
Micro mirror photo.
Fig. 3 is the voltage-temperature relationship comparison that the graphene composite heating silk prepared in carbon fiber and embodiment 1 is commercialized
Figure.
Fig. 4 is the conduction time-temperature relation that the graphene composite heating silk prepared in carbon fiber and embodiment 1 is commercialized
Comparison diagram.
Fig. 5 is the power temperature relationships comparison that the graphene composite heating silk prepared in carbon fiber and embodiment 1 is commercialized
Figure.
Specific embodiment
Following embodiment, which is merely, further illustrates the present invention, in the case where not violating purport of the invention, the present invention
It should be not limited to the content that following experimental example is specifically expressed.
It is raw materials used as follows:
Single-layer graphene, Suzhou Heng Qiu graphene Co., Ltd；Multilayer (6-10 layers) graphene；Figure spirit evolution section, Shenzhen
Skill Co., Ltd；The concentrated sulfuric acid, Shanghai Aladdin reagent Co., Ltd；Concentrated nitric acid, Shanghai Aladdin reagent Co., Ltd；Ethyl alcohol,
Shanghai Aladdin reagent Co., Ltd；Acetone, Shanghai Aladdin reagent Co., Ltd；Silane coupling agent (KH550), Hangzhou Jesse
Block Chemical Co., Ltd.；Titanate coupling agent (TCA-L38), Nanjing Neng De new material technology Co., Ltd；Polycarbonate
(2856), Bayer (China) Co., Ltd. Shanghai branch company；Polystyrene (PG-33), Zhenjiang Qi Mei Chemical Co., Ltd.；Diformazan
Benzene, Shanghai Aladdin reagent Co., Ltd；Tetrahydrofuran, Shanghai Aladdin reagent Co., Ltd；Carbon fiber (T700SC-6000-
50C) toray Industrial Co., Ltd；Carbon fiber (T700SC-24000-50C), toray Industrial Co., Ltd.
Embodiment 1
The preparation of graphene composite heating silk, preparation flow figure are as shown in Figure 1.
20 parts of single-layer graphenes are placed in 400 parts of concentrated acids (the 98wt% concentrated sulfuric acid: 70wt% concentrated nitric acid=3:1, volume ratio)
In, ultrasound 2 hours, are heated to reflux 3 hours under the conditions of 80 DEG C, mixed liquor are diluted repeatedly, is filtered, product under the conditions of 60 DEG C
In 70 DEG C of vacuum drying ovens after drying 12 hours, functionalization graphene is obtained.By 20 parts of functionalization graphenes and 2000 parts of ethyl alcohol
It is configured to solution, ultrasound 1 hour under the conditions of 60 DEG C is added 1 part of silane coupling agent (KH550) and stirs 12 hours, afterwards 70
Solution is completely dried in DEG C vacuum drying oven, obtains silicane coupling agent surface grafted graphene.Then, by 20 parts of surface graftings
The graphene of silane coupling agent and 100 parts of polycarbonate (2856) are added in 150 parts of tetrahydrofurans, stir 3 under the conditions of 50 DEG C
Hour, it is configured to graphene/polymer resin compounded slurry.Commercialization carbon fiber (T700SC-6000-50C) is dipped in graphite
It is taken out after 2 hours in alkene/macromolecule resin composite mortar, it will be in graphene/polymer resin compounded slurry under the conditions of 70 DEG C
Solvent volatilization it is dry, obtain the carbon fiber of surface cure graphene/polymer resin compounded slurry.Finally, in a nitrogen atmosphere,
The carbon fiber of surface cure graphene/polymer resin compounded slurry is placed in the charing of tube furnace high temperature under the conditions of 600 DEG C
Processing, obtains graphene composite heating silk.
Graphene composite heating silk prepared by carbon fiber (T700SC-6000-50C) and the present embodiment 1 will be commercialized to pass through
Scanning electron microscope (250 FEG of QUANTA) carries out morphology observation, as shown in Fig. 2, Fig. 2 (A) is commercialization carbon fiber scanning
Electron micrograph, fiber surface is smooth, and substantially without attachment, Fig. 2 (B) is the graphene composite heating that embodiment 1 obtains
Silk electron scanning micrograph, it can be seen that graphene and amorphous nanocarbon particle are evenly coated at carbon fiber surface.
Fig. 3 is that graphene composite heating silk prepared by carbon fiber (T700SC-6000-50C) and the present embodiment 1 is commercialized
Voltage-temperature relationship comparison diagram, as seen from the figure, under conditions of identical applied voltage, the surface temperature of graphene composite heating silk
Degree is apparently higher than commercialization carbon fiber, and temperature difference shows graphene composite heating silk prepared by the present invention at 5-10 DEG C or so
With higher heating efficiency.
Fig. 4 is that graphene composite heating silk prepared by carbon fiber (T700SC-6000-50C) and the present embodiment 1 is commercialized
Conduction time-temperature relation comparison diagram, wherein applied voltage 6V, as seen from the figure, and under identical conduction time, graphene
Composite heating silk has higher surface temperature, and heating rate is faster, illustrates graphene composite heating silk prepared by the present invention
With higher heating efficiency.
Fig. 5 is that graphene composite heating silk prepared by carbon fiber (T700SC-6000-50C) and the present embodiment 1 is commercialized
Power temperature relationships comparison diagram, as seen from the figure, in the case where reaching identical surface temperature condition, graphene composite heating silk needs
Power it is lower, when needing to reach 45 DEG C, power required for graphene composite heating silk will than be commercialized carbon fiber
(T700SC-6000-50C) the low 2.5W of power needed for has lower energy consumption, energy saving.
Embodiment 2
15 parts of multi-layer graphenes are placed in 500 parts of 98wt% concentrated sulfuric acids, ultrasound 1 hour under the conditions of 50 DEG C, at 70 DEG C
Under the conditions of be heated to reflux 2 hours, mixed liquor is diluted repeatedly, is filtered, product after dry 12 hours, obtains in 60 DEG C of vacuum drying ovens
To functionalization graphene.15 parts of functionalization graphenes and 1500 parts of acetone are configured to solution, ultrasound 2 is small under the conditions of 60 DEG C
When, 2 parts of titanate coupling agents (TCA-L38) are added afterwards and stir 6 hours, are completely dried solution in 60 DEG C of vacuum drying ovens,
Obtain the modified graphene of surface grafting titanate coupling agent.Then, by the modification stone of 15 parts of surface grafting titanate coupling agents
Black alkene and 80 parts of polystyrene (PG-33) are added in 100 parts of dimethylbenzene, stir 2 hours under the conditions of 60 DEG C, are configured to graphite
Alkene/macromolecule resin composite mortar.Carbon fiber (T700SC-24000-50C) is dipped in graphene/polymer resin compounded slurry
In taken out after 3 hours, the solvent in graphene/polymer resin compounded slurry volatilized under the conditions of 80 DEG C dry.Finally, in nitrogen
Under gas atmosphere, the carbon fiber after coating is placed in tube furnace high temperature charing process under the conditions of 550 DEG C, it is compound to obtain graphene
Heating wire.
The result shows that graphene composite heating prepared by graphene composite heating silk and embodiment 1 prepared by the present embodiment 2
The similar performance of silk, under conditions of identical applied voltage, surface temperature is apparently higher than commercialization carbon fiber (T700SC-
24000-50C)；Under identical conduction time and applied voltage, graphene composite heating silk and commercialization prepared by embodiment 2
Carbon fiber (T700SC-24000-50C) is compared, and has higher surface temperature and heating rate；Graphene prepared by embodiment 2
Composite heating silk is compared with being commercialized carbon fiber (T700SC-24000-50C), in the case where reaching identical surface temperature condition,
With lower energy consumption.
Embodiment 3
10 parts of multi-layer graphenes are placed in 300 parts of concentrated nitric acids, ultrasound 2 hours under the conditions of 60 DEG C, under the conditions of 70 DEG C
It is heated to reflux 2 hours, mixed liquor is diluted repeatedly, is filtered, after product is 6 hours dry in 60 DEG C of vacuum drying ovens, obtain function
Graphite alkene.10 parts of functionalization graphenes and 1500 parts of ethyl alcohol are configured to solution, ultrasound 2 hours under the conditions of 60 DEG C are rear to add
Enter 0.5 part of silane coupling agent (KH550) and stir 6 hours, solution is completely dried in 60 DEG C of vacuum drying ovens, obtains to surface and connects
The modified graphene of branch silane coupling agent.Then, 10 parts of modified graphenes and 50 parts of polystyrene (PG-33) are added 50 part two
In toluene, is stirred 2 hours under the conditions of 60 DEG C, be configured to graphene/polymer resin compounded slurry.By carbon fiber (T700SC-
It 24000-50C) is dipped in graphene/polymer resin compounded slurry and is taken out after 1 hour, by graphene/height under the conditions of 80 DEG C
Solvent volatilization in molecule resin compounded slurry is dry.Finally, in a nitrogen atmosphere, by the carbon fiber after coating in 400 DEG C of conditions
Under be placed in tube furnace high temperature charing process, obtain graphene composite heating silk.
The result shows that graphene composite heating prepared by graphene composite heating silk and embodiment 1 prepared by the present embodiment 3
The similar performance of silk, under conditions of identical applied voltage, surface temperature is apparently higher than commercialization carbon fiber (T700SC-
24000-50C)；Under identical conduction time and applied voltage, graphene composite heating silk and commercialization prepared by embodiment 3
Carbon fiber (T700SC-24000-50C) is compared, and has higher surface temperature and heating rate；Graphene prepared by embodiment 2
Composite heating silk is compared with being commercialized carbon fiber (T700SC-24000-50C), in the case where reaching identical surface temperature condition,
With lower energy consumption.
Claims (9)
1. a kind of graphene composite heating silk, which is characterized in that the graphene composite heating silk include carbon fiber, graphene and
Amorphous nanocarbon particle, wherein the graphene and amorphous nanocarbon particle are coated on the surface of carbon fiber.
2. a kind of preparation method of graphene composite heating silk according to claim 1, which is characterized in that including walking as follows
It is rapid:
(1) graphene is placed in concentrated acid, then heating ultrasound carries out back flow reaction, then be diluted, filter, dry, obtains
Functionalization graphene；
(2) above-mentioned functionalization graphene is dispersed in dispersion liquid, obtains graphene solution, heating is ultrasonic, adds under stirring condition
Enter coupling agent, heated under vacuum to dispersion liquid evaporating completely obtains the graphene of surface grafting coupling agent；
(3) graphene of surface grafting coupling agent and macromolecule resin are added in organic solvent, heating stirring obtains graphite
Alkene/macromolecule resin composite mortar takes out then by impregnated carbon fiber in the graphene/polymer resin compounded slurry
Carbon fiber, heating, obtains the carbon fiber of surface cure graphene/polymer resin compounded slurry；
(4) under nitrogen atmosphere, the carbon fiber of above-mentioned surface cure graphene/polymer resin compounded slurry is carried out at carbonization
Reason, obtains graphene composite heating silk.
3. a kind of preparation method of graphene composite heating silk according to claim 2, which is characterized in that the graphite
Alkene, concentrated acid, dispersion liquid, coupling agent, macromolecule resin, organic solution and carbon fiber, according to the mass fraction are as follows:
4. a kind of preparation method of graphene composite heating silk according to claim 2, which is characterized in that in step (1)
The temperature of the back flow reaction is 60-80 DEG C, reaction time 2-3h；The temperature of heating described in step (1)~step (3) is
40-70℃；The ultrasonic time described in step (1) and step (2) is 1-2h.
5. a kind of preparation method of graphene composite heating silk according to claim 2, which is characterized in that in step (2)
The time of the stirring is 10-12h；The time of stirring described in step (3) is 1-3h, and the time of the dipping is 1-3h；Step
Suddenly carbonization treatment described in (4) is to be placed in tube furnace at 400-600 DEG C to carry out calcining 2-3h.
6. a kind of preparation method of graphene composite heating silk according to claim 2, which is characterized in that in step (1)
The concentrated acid is the mixture of one or both of the concentrated sulfuric acid and concentrated nitric acid.
7. a kind of preparation method of graphene composite heating silk according to claim 2, which is characterized in that in step (2)
The coupling agent is one of silane coupling agent, titanate coupling agent, organochromium complexes coupling agent and aluminate coupling agent
Or it is a variety of, the dispersion liquid is distilled water, ethyl alcohol or acetone.
8. a kind of preparation method of graphene composite heating silk according to claim 2, which is characterized in that in step (3)
Macromolecule resin be selected from one of polystyrene, polycarbonate, polyamide, polyimides and polymethyl methacrylate
Or it is several.
9. a kind of preparation method of graphene composite heating silk according to claim 2, which is characterized in that in step (3)
The organic solvent is in benzene,toluene,xylene, tetrahydrofuran, acetone, dimethylformamide, ethyl acetate and petroleum ether
It is one or more.
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| CN111405692A (en) * | 2020-04-10 | 2020-07-10 | 陈东亮 | Graphene heating wire processing system and method |
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Application publication date: 20190705 |