CN105692600A - Preparation method of super-soft and lightweight graphene electro-thermal film - Google Patents
Preparation method of super-soft and lightweight graphene electro-thermal film Download PDFInfo
- Publication number
- CN105692600A CN105692600A CN201610049789.9A CN201610049789A CN105692600A CN 105692600 A CN105692600 A CN 105692600A CN 201610049789 A CN201610049789 A CN 201610049789A CN 105692600 A CN105692600 A CN 105692600A
- Authority
- CN
- China
- Prior art keywords
- graphene
- film
- graphite
- temperature
- graphene oxide
- 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
- 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
- C01B2204/22—Electronic properties
-
- 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
- C01B2204/24—Thermal properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a preparation method of a super-soft and lightweight graphene electro-thermal film. A film is formed through assembling an ultra-large fragment-free graphene oxide solution, and a graphene sheet layer structure is repaired at a high temperature, so that inner defects of the graphene film are controlled to the greatest extent. The graphene film can realize rapid response to a high temperature of 25 DEG C to 1500 DEG C within a very short time of 1 second to 10 seconds under the voltage of 1V to 10V; the temperature rising and decreasing speed is 600 DEG C/s to 2000 DEG C/s. Meanwhile, the graphene electro-thermal film has a lot of folds and has extremely good flexibility, so that the graphene electro-thermal film is applicable to various types of flexible devices. Therefore, the graphene electro-thermal film is simple in structure and can be prepared in a large area and a large batch; the graphene electro-thermal film has the advantages of safe working voltage, high thermal conversion efficiency, good thermal conductivity, rapid response, capability of accurately controlling the temperature and good toughness, and can be used for different application environments.
Description
Technical field
The present invention relates to flexible electric heating material, the preparation method particularly relating to a kind of super soft light graphite alkene Electric radiant Heating Film。
Background technology
Two dimensional crystal material Graphene (graphene) being made up of single carbon atom layer, is the thinnest in known materials, is referred to as the material of mystery, has started global research boom。Graphene has excellent electric property, and (under room temperature, electron mobility is up to 2 × 105cm2/ Vs), prominent heat conductivility (5000W/ (mK), extraordinary specific surface area (2630m2/ g), its Young's modulus (1100GPa) and fracture strength (125GPa)。AndreGeim and KonstantinNovoselov is because obtaining Nobel prize for physics in 2010 to the contribution of Graphene research。The electrical and thermal conductivity performance of Graphene excellence is well beyond metal, and Graphene has the advantage of corrosion-and high-temp-resistant simultaneously, and its good mechanical performance and relatively low density more allow it possess the potentiality at thermo electric material field substituted metal。Owing to Graphene large-scale processing is increasingly becoming reality, graphene film by substituted metal materials application in different fields。
The conventional electrical resistor heating element in electric heating system is generally adopted the materials such as metal forming, film coating, resistance wire, wire netting。The heating element heater employed up to is nichrome。But, for nichrome, still seem not enough at present in the following areas: the density of nichrome is more than 8g/cm3, and during use, thickness has several millimeters；Resistivity low (～10 6 Ω/m), however it remains electric heating conversion efficiency low, the rate of heat addition is little, and heating element heater does not have automatic constant-temperature and power back-off function so that electric heating system structure is complicated, the weak points such as thermal inertia is big；Ferrum-chromium-aluminum is Alfer, there is the high-temperature brittleness of cold-shortness, 475 DEG C of fragility and more than 1000 DEG C, and the elevated temperature strength that causes due to high-temperature brittleness is low, and to ultimately result in heating short for service life；The solderability of alloy is very poor, difficult reparation。
And the Graphene Electric radiant Heating Film reported at present has two kinds, one is graphene oxide Electric radiant Heating Film, utilizes its resistance heating, but its structural instability, and there is very great fluctuation process in its heating being, uncontrollable；It two is graphite film or the polyimide film fired, but its flexibility is limited, finite number of time folding after will be damaged。
On the whole, thermo electric material that exploitation is stable, that quick that respond, lightweight, high flexibility and wide scope is suitable for it is badly in need of at present。
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation method of a kind of super soft light graphite alkene Electric radiant Heating Film。
It is an object of the invention to be achieved through the following technical solutions: the preparation method of a kind of super soft light graphite alkene Electric radiant Heating Film, step is as follows:
(1) it being the average-size of 4-20mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, solidification liquid or liquid nitrogen stop the 10-100 second, it is frozen into graphene oxide gel film, graphene oxide gel film is put into the refrigerator of-4～-20 DEG C freezes quick freezing in 1-12h or liquid nitrogen。
(2) by step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 0.1-4 DEG C/min under atmosphere of inert gases, insulation 0.5-1h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 2-4 DEG C/min, is incubated 1-4h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 2-4 DEG C/min, insulation 1-2h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating。
(3), after being suppressed by aerogel film high pressure, pressure is 10-100MP, obtains the Graphene Electric radiant Heating Film of uniform closely knit flexibility。
Further, described rate of extrusion is between 4-20m/min。
Further, the temperature of described solidification liquid is 30-60 DEG C, is made up of according to arbitrarily ratio one or more in methanol, ethanol, ethyl acetate, n-butyl alcohol, ethylene glycol, Ketohexamethylene, glycerol, butyl acetate, propylene glycol, n-propyl acetate, acetic acid, glycerol, isobutanol, methyl acetate etc.。
Further, in described step 1, the average-size graphene oxide more than 100um obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 orders is filtered, and obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, is added dropwise over hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes (namely the potassium permanganate in mixed liquor is removed completely)；
(3) mixed liquor after processing to step 2 is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped graphite oxide disappears, then goes out graphite oxide wafer with the screen filtration of 140 orders；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20～80 turns/min, concussion washing so that graphite oxide wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, and average-size is more than 100um, and breadth coefficient is between 0.2-0.5。
Further, Modified-Hummer method in described step 1 is particularly as follows: at-10 DEG C, potassium permanganate is completely dissolved in the concentrated sulphuric acid that mass fraction is 98%, add graphite, stirring is stopped after 60 revs/min of stirring 2h, under low temperature (-10-20 DEG C), react 6-48h, obtain the oxidized graphite flake reactant liquor of wide distribution；Described graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1g:2-4g:30-40ml, the granularity of graphite is more than 150 μm。
Further, described mesh screen is the acidproof mesh screens such as titanium alloy。
Further, in described step 1, the reactant liquor of oxidized graphite flake is diluted by diluent such as concentrated sulphuric acids, and the volume of diluent is 1-10 times of reactant liquor volume。
The present invention compared with prior art has the advantages that 1) primary raw materials of graphene oxide is graphite, raw material sources extensively, be easy to get, with low cost；2) graphene film is carbon-based material, and density is only at 1.8-2.1g/cm3, light weight, it is possible to large area uses；3) graphene film has fine toughness, it is possible to arbitrarily bends and keeps good electric conductivity, have high machinability, is conducive to the demand of the application variously-shaped, various adapted to；4) Graphene Electric radiant Heating Film has extremely low resistivity, the ultrafast rate of heat addition, high heat conductivity and quick heat radiating capability, almost without thermal inertia, can conduct heat to rapidly other materials；5) heat conduction is fast, and homogeneous temperature is stable, long service life；6) graphene film thickness, area, shape and size are controlled, are suitable for row wide；7) Graphene Electric radiant Heating Film startup voltage and running voltage are low, it is possible to work below human safety voltage；8) the own steady chemical structure of Graphene Electric radiant Heating Film, applicable interval is extremely wide, all applicable from native country continent to the outer space；9) Graphene Electric radiant Heating Film tolerance to cold is significantly high, even if at very low temperature, still has well flexible and can well work。
Detailed description of the invention
A kind of super soft light graphite alkene Electric radiant Heating Film of the present invention, is assembled without fragment graphene oxide solution by super large sheet；Through 3000 DEG C of high-temperature process, its internal graphene film Rotating fields is perfect to be repaired so that Graphene Electric radiant Heating Film has high electrical conductivity, and programming rate is exceedingly fast；Inside has the orientation of height, and graphene sheet layer is parallel with graphene film, and the degree of orientation reaches more than 94%；Film surface and inside have many random stretchable folds so that it has significantly high flexibility and draftability；Have passed through high pressure briquetting process, its structure is closely knit, but owing to carbonaceous itself is relatively light, therefore its density is relatively low；The heat conductivity of film own is good, and therefore it has fabulous rate of temperature fall；Mutually overlap through the pi-conjugated effect of π inside described Graphene Electric radiant Heating Film so that it has good intensity；This body structure of film is extremely stable, and equalizing section compole is wide。
By the present invention in that by super large sheet graphene oxide film forming, the wherein average-size of the planar orientation graphene film more than 100 μm important role in the process constituting graphene film of the present invention, the present invention, before graphite oxide crystal is washed, adopts the way of mesh screen separation, chip separation is gone out。And adopting 10 times to be diluted with the frozen water of upper volume so that its wafer will not be destroyed because of the heat of solution of sulphuric acid。Adopt shaking table concussion washing further so that graphene oxide lamella avoids the broken of mechanical force when peeling off。Further, the present invention prepares graphene film also by cryogenic conditions, at low temperatures, potassium permanganate oxidation is more weak, the speed that its selfdecomposition produces oxygen is slow, and therefore gas is just very weak to the fragmentation of graphite oxide crystal so that the graphene oxide of big lamella is preserved。And course of reaction and cleaning process do not have violent stirring and ultrasonic procedure, therefore lamella there is no broken。Comprehensive above some, we obtain the graphene oxide without fragment of super large sheet, and average-size is more than 87um, and breadth coefficient is between 0.2-0.5, and shive content is lower than 1%。
The preparation facilities with in-line outlet used in the present invention is prior art, and it is rectangular structure, and centre has in-line die orifice, and described in-line die orifice is a runner become narrow gradually。The runner become narrow gradually can be effectively increased the flow field active force to graphene film, is conducive to the formation of the regular orientation texture of graphene dispersion system。
The present embodiment is served only for that the present invention is described further, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art makes some nonessential change and adjustment according to the content of foregoing invention, belongs to protection scope of the present invention。
Embodiment 1: without the preparation of the graphene oxide of fragment super large sheet
Embodiment 1-1
(1) potassium permanganate is slowly added in the concentrated sulphuric acid of quickly stirring at-10 DEG C, after fully dissolving, add graphite, 60 revs/min be slowly stirred 2h after stop stirring, at 20 DEG C, 50 DEG C, react 6h respectively, respectively obtain the graphite oxide crystal of wide distribution；All there is more fragment in the graphite oxide wafer obtained at two kinds of temperature, this makes the graphene oxide of its correspondence have a lot of fragments equally。
(2) (extension rate can be any multiple to reactant liquor diluting concentrated sulfuric acid step 1 obtained, the present embodiment dilutes about 10 times), and with the titanium alloy mesh screen of 150um aperture (140 order), graphite oxide crystal is filtered out (reactant liquor recovery), and it is poured slowly in the frozen water relative to 10 times of volumes of filtration product of quickly stirring, stand 2h, it is slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then filter out graphite oxide wafer with titanium alloy mesh screen (140 order)；Shaking table slowly shakes washing, obtains the graphene oxide without fragment super large sheet (average-size is 87um, and breadth coefficient is 0.5)。Graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1g:2g:40ml, the granularity of graphite is 200um。
After the lower reaction of high temperature 50 degree, isolated graphite oxide wafer washs, after separating, the graphene oxide obtained a lot of fragments equally；Large stretch of graphene oxide distribution of sizes uniform concentration more after (20 DEG C) Reaction Separation under low temperature, shive content is few。
Embodiment 1-2
Potassium permanganate is slowly added in the concentrated sulphuric acid of quickly stirring at-10 DEG C, after fully dissolving, adds graphite, 60 revs/min be slowly stirred 2h after stop stirring, under low temperature (0 DEG C), react 48h, obtain reactant liquor；Reactant liquor is diluted with the dilute sulfuric acid that the concentrated sulphuric acid of mass fraction more than 98%, mass fraction are 10% respectively, then with the titanium alloy mesh screen in 150um aperture, graphite oxide crystal is filtered out (reactant liquor recovery), and it is poured slowly in the frozen water relative to 10 times of volumes of filtration product of quickly stirring, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then leach graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains product。Graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1:4g:30ml；The granularity of graphite is 500um。
Adopt diluting concentrated sulfuric acid, the graphene oxide of the super large without fragment being obtained by reacting sheet (average-size is 98um, breadth coefficient 0.4), and dilute with dilute sulfuric acid, the product obtained contains a large amount of fragments, distribution of sizes coefficient is more than 100%。This is due in dilute sulfuric acid dilution, highly exothermic, destroys graphite oxide crystal。
Embodiment 1-3
Potassium permanganate is slowly added in the concentrated sulphuric acid of quickly stirring at-10 DEG C, after fully dissolving, adds graphite, 60 revs/min be slowly stirred 2h after stop stirring, under low temperature (20 DEG C), react 28h, obtain the graphite oxide crystal of wide distribution；By reactant liquor diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um aperture, graphite oxide crystal is filtered out (reactant liquor recovery), and be poured slowly into respectively quickly stirring relative to 5 times of volumes of filtration product, 8 times of volumes, 10 times of volumes frozen water in, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then leach graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains product；Graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1:5g:34ml, the granularity of graphite is 2mm。
Experimental result shows, the frozen water of 5 times of volumes and 8 times of volumes all can not the graphene film obtaining size uniformity, under 10 times of volumes, just can obtain graphene oxide without fragment super large sheet (average-size is 92um, breadth coefficient 0.2)。It follows that the amount of frozen water is too low, the heat of mixing will be made to concentrate release, destroy crystal structure。
Embodiment 2: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares prepares flexible light weight Graphene Electric radiant Heating Film。
By certain density super large sheet without fragment graphene oxide (average-size is 150um) aqueous solution from have in-line outlet preparation facilities (device is rectangular structure, centre has an in-line die orifice become narrow gradually) in continuously and smoothly extrusion after enter solidification liquid a period of time, it is frozen into graphene oxide gel film, puts in refrigerator and slowly freeze or quick freezing in liquid nitrogen。Described super large sheet without the concentration of fragment graphene oxide solution between 100mg/mL。It is between 10m/min that described continuously and smoothly extrudes into the speed of solidification liquid, and temperature is 30 DEG C。Described solidification liquid is liquid nitrogen。In described solidification liquid, the time of staying is 100 seconds。
With obtaining graphite oxide aerogel thin film after lyophilization or supercritical drying, sending in high temperature furnace and carry out high-temperature heat treatment, processing mode is such as shown in table 1～3, and after then being suppressed by its high pressure, pressure is 50MP, obtains Graphene Electric radiant Heating Film。
Table 1
Table 2
Table 3
From table 1～table 3 it can be seen that the performance of this material mainly has two aspects to determine, one material internal graphene oxide sheet structure repair situation, i.e. the coming off and the reparation of carbon conjugated structure under high temperature of functional group。Its two, the seriality of material internal orientation texture, the i.e. connectivity of internal sheets Rotating fields。The two combined effect is to increase the performance of graphene film。
In table 1, compare A B C D the temperature of E, A too low, be not enough to remove the functional group that major part is degradable, cause that in second step pyroprocess, gas quickly produces in a large number, at high temperature tearing sheet Rotating fields；E temperature is too high, produces gas too fast, both can make deterioration in material properties。Having only at BCD temperature, functional group can slowly and thoroughly remove, to ensure material property。Relatively C F G H, F heating rate too low, gas release is excessively slow；H temperature-rise period is too fast, and gas release is too fast, tears material internal structure, is unfavorable for forming conductive channel。Relatively C I J K L M, I temperature retention time too short, it is impossible to ensure the degraded of major part functional group；M insulating process is long, can absorb the tar inside stove, is unfavorable for the lifting of performance。JKL, owing to avoiding above 2 points, has good electric heating property and bending performance。
In table 2, compare A B C D too low being not enough to of E, A heating rate form small gap structure, have a strong impact on electric heating property。E programming rate is too high, can tear Graphene interlayer structure so that graphene film electric heating property is deteriorated。Have only under the programming rate of BCD, just can the capable seriality both ensured within graphene film。Relatively C F G H, F temperature too low so that stable functional group can not be sufficiently disengaged from, easy transition release gas in follow-up graphited process, the stable formation of destruction graphene-structured；H temperature is too high, has reached graphitization temperature, and when now gas release, its temperature is also not enough to maintain the formation of conductive network, and the micro-airbag structure now formed is imperfect；Relatively C I J K L M, I temperature retention time too short, stable functional group can not fully come off；M overlong time, the easy tar adsorption of graphene film, it is unfavorable for the lifting of film properties；And when CJK, both can ensure that fully coming off of stabilising functional group, it is avoided that again the puzzlement of tar。
In table 3, compare A B C D E, A heating rate too low, it is excessively slow that most stabilising functional group comes off；E temperature-rise period is too fast, and gas release and high-temperature expansion are too fast, it is easy to destroy graphene-structured。Only when BCD, the structure on Graphene could be repaired slowly。Relatively C F G H I, F outlet temperature too low, graphene-structured reparation is perfect not, so various performance is all very poor；I outlet temperature is too high, and Graphene can be vaporized；Could both ensure the reparation of graphene-structured at the temperature of CGH, and will not be vaporized again and compare。C J K L M, J temperature retention time too low, graphene-structured can not fully be repaired, and M temperature retention time is long, also can make absorption body of heater in tar, affect electric heating and the bending performance of film。
Claims (7)
1. the preparation method of a super soft light graphite alkene Electric radiant Heating Film, it is characterised in that step is as follows:
(1) it being the average-size of 4-20mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, solidification liquid or liquid nitrogen stop the 10-100 second, it is frozen into graphene oxide gel film, graphene oxide gel film is put into the refrigerator of-4～-20 DEG C freezes quick freezing in 1-12h or liquid nitrogen。
(2) by step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 0.1-4 DEG C/min under atmosphere of inert gases, insulation 0.5-1h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 2-4 DEG C/min, is incubated 1-4h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 2-4 DEG C/min, insulation 1-2h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating。
(3), after being suppressed by aerogel film high pressure, pressure is 10-100MP, obtains the Graphene Electric radiant Heating Film of uniform closely knit flexibility。
2. the method for claim 1, it is characterised in that described rate of extrusion is between 4-20m/min。
3. the method for claim 1, it is characterized in that, the temperature of described solidification liquid is 30-60 DEG C, is made up of according to arbitrarily ratio one or more in methanol, ethanol, ethyl acetate, n-butyl alcohol, ethylene glycol, Ketohexamethylene, glycerol, butyl acetate, propylene glycol, n-propyl acetate, acetic acid, glycerol, isobutanol, methyl acetate etc.。
4. the method for claim 1, it is characterised in that in described step 1, the average-size graphene oxide more than 100um obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 orders is filtered, and obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, is added dropwise over hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes (namely the potassium permanganate in mixed liquor is removed completely)；
(3) mixed liquor after processing to step 2 is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped graphite oxide disappears, then goes out graphite oxide wafer with the screen filtration of 140 orders；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20～80 turns/min, concussion washing so that graphite oxide wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, and average-size is more than 100um, and breadth coefficient is between 0.2-0.5。
5. method according to claim 4, it is characterized in that, Modified-Hummer method in described step 1 is particularly as follows: at-10 DEG C, potassium permanganate is completely dissolved in the concentrated sulphuric acid that mass fraction is 98%, add graphite, stop stirring after 60 revs/min of stirring 2h, under low temperature (-10-20 DEG C), react 6-48h, obtain the oxidized graphite flake reactant liquor of wide distribution；Described graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1g:2-4g:30-40ml, the granularity of graphite is more than 150 μm。
6. method according to claim 4, it is characterised in that described mesh screen is the acidproof mesh screens such as titanium alloy。
7. method according to claim 4, it is characterised in that in described step 1, the reactant liquor of oxidized graphite flake is diluted by diluent such as concentrated sulphuric acids, and the volume of diluent is 1-10 times of reactant liquor volume。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610049789.9A CN105692600B (en) | 2016-01-25 | 2016-01-25 | A kind of preparation method of super soft light graphite alkene Electric radiant Heating Film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610049789.9A CN105692600B (en) | 2016-01-25 | 2016-01-25 | A kind of preparation method of super soft light graphite alkene Electric radiant Heating Film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105692600A true CN105692600A (en) | 2016-06-22 |
| CN105692600B CN105692600B (en) | 2017-10-10 |
Family
ID=56228678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610049789.9A Active CN105692600B (en) | 2016-01-25 | 2016-01-25 | A kind of preparation method of super soft light graphite alkene Electric radiant Heating Film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105692600B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106154022A (en) * | 2016-07-05 | 2016-11-23 | 浙江大学 | A kind of breathe graphene film detection voltage stability in application |
| CN106185903A (en) * | 2016-07-15 | 2016-12-07 | 浙江大学 | A kind of method of ice crystal auxiliary preparation high flexibility graphene film |
| CN106332327A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Preparation method for composite graphene electrothermal film |
| CN107555419A (en) * | 2017-10-13 | 2018-01-09 | 杭州高烯科技有限公司 | A kind of low corrugation density graphene film and preparation method thereof |
| CN107758644A (en) * | 2017-10-13 | 2018-03-06 | 杭州高烯科技有限公司 | A kind of method that super-pressure thermal reduction prepares graphene film |
| CN108461309A (en) * | 2018-04-25 | 2018-08-28 | 山西大学 | A kind of preparation method of graphene film electrode material |
| KR20200002903A (en) * | 2017-04-11 | 2020-01-08 | 항저우 고우시 테크놀로지 컴퍼니 리미티드 | Flexible graphene film and its manufacturing method |
| CN111944497A (en) * | 2019-05-16 | 2020-11-17 | 常州第六元素材料科技股份有限公司 | Graphene oxide composite carbon source mixture and preparation method thereof, graphene heat-conducting film and preparation method thereof |
| CN112210250A (en) * | 2020-09-29 | 2021-01-12 | 兰州大学 | Preparation method of graphene-based screen printing electrothermal ink |
| CN114702030A (en) * | 2022-05-18 | 2022-07-05 | 山东大学 | Preparation method of ultrathin flexible graphene film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229782A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of ordered graphene porous membrane |
| CN104229783A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene film with high thermal conductivity |
-
2016
- 2016-01-25 CN CN201610049789.9A patent/CN105692600B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229782A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of ordered graphene porous membrane |
| CN104229783A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene film with high thermal conductivity |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106154022A (en) * | 2016-07-05 | 2016-11-23 | 浙江大学 | A kind of breathe graphene film detection voltage stability in application |
| CN106185903A (en) * | 2016-07-15 | 2016-12-07 | 浙江大学 | A kind of method of ice crystal auxiliary preparation high flexibility graphene film |
| CN106332327A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Preparation method for composite graphene electrothermal film |
| KR20200002903A (en) * | 2017-04-11 | 2020-01-08 | 항저우 고우시 테크놀로지 컴퍼니 리미티드 | Flexible graphene film and its manufacturing method |
| KR102284825B1 (en) | 2017-04-11 | 2021-08-02 | 항저우 고우시 테크놀로지 컴퍼니 리미티드 | Flexible graphene film and its manufacturing method |
| CN107555419A (en) * | 2017-10-13 | 2018-01-09 | 杭州高烯科技有限公司 | A kind of low corrugation density graphene film and preparation method thereof |
| CN107758644A (en) * | 2017-10-13 | 2018-03-06 | 杭州高烯科技有限公司 | A kind of method that super-pressure thermal reduction prepares graphene film |
| CN108461309A (en) * | 2018-04-25 | 2018-08-28 | 山西大学 | A kind of preparation method of graphene film electrode material |
| CN111944497A (en) * | 2019-05-16 | 2020-11-17 | 常州第六元素材料科技股份有限公司 | Graphene oxide composite carbon source mixture and preparation method thereof, graphene heat-conducting film and preparation method thereof |
| CN111944497B (en) * | 2019-05-16 | 2022-02-22 | 常州第六元素材料科技股份有限公司 | Graphene oxide composite carbon source mixture and preparation method thereof, graphene heat-conducting film and preparation method thereof |
| CN112210250A (en) * | 2020-09-29 | 2021-01-12 | 兰州大学 | Preparation method of graphene-based screen printing electrothermal ink |
| CN114702030A (en) * | 2022-05-18 | 2022-07-05 | 山东大学 | Preparation method of ultrathin flexible graphene film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105692600B (en) | 2017-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105692600A (en) | Preparation method of super-soft and lightweight graphene electro-thermal film | |
| CN105731436B (en) | Pure graphene aerogel film of continuous ultralight rule orientating and preparation method thereof | |
| CN108251076B (en) | Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof | |
| WO2017084606A1 (en) | Method for directly preparing expanded graphite or graphene under normal temperature and normal pressure | |
| CN105752963B (en) | A kind of foldable electrothermal film device based on graphene | |
| CN105731435B (en) | A kind of high tensile flexible graphene composite heat conduction film and preparation method thereof | |
| CN105731434B (en) | A kind of efficient and light weight electromagnetic shielding graphene film and preparation method thereof | |
| CN105006375B (en) | The porous CNT of a kind of nitrogen, phosphor codoping, preparation method and application | |
| CN105523547A (en) | Graphene film with ultrahigh flexibility and high thermal conductivity and preparation method of graphene film | |
| WO2017128929A1 (en) | Method for preparing graphene dispersion and article thereof | |
| CN110804420B (en) | Phase-change composite material based on high-thermal-conductivity anisotropic graphene framework and preparation method thereof | |
| CN103420352A (en) | High-fluoride-content graphite fluoride and preparation method thereof | |
| CN104445153B (en) | A kind of method being prepared charcoal nanometer roll by Graphene magnanimity | |
| WO2016173111A1 (en) | Graphene dispersing agent and preparation method therefor | |
| WO2016011905A1 (en) | Silver-doped graphene composite paper and preparation method therefor | |
| CN104401977A (en) | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel | |
| CN102464313A (en) | Preparation method of graphene | |
| CN107697911B (en) | Method for preparing natural graphite heat dissipation film from graphite oxide | |
| CN102320598A (en) | Preparation method of graphene | |
| CN103613093B (en) | A kind of hydrogen reducing prepares the method for Graphene | |
| CN104466204A (en) | Array carbon nano-tube/graphene platinum-supported catalyst for fuel cell and preparation method of array carbon nano-tube/graphene platinum-supported catalyst | |
| CN102765716A (en) | Preparation method of graphene | |
| CN105565300A (en) | Method for preparing graphene films with high heat conductivity | |
| CN103420365A (en) | Graphene preparation method | |
| CN106115697B (en) | A kind of preparation method of active carbon of the surface rich in petal-shaped graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190910 Address after: 313100 Room 830, 8th Floor, Changxing World Trade Building, 1278 Mingzhu Road, Changxing Economic Development Zone, Huzhou City, Zhejiang Province Patentee after: Changxin de Technology Co., Ltd. Address before: 310058 Xihu District, Zhejiang, Yuhang Tong Road, No. 866, No. Patentee before: Zhejiang University |
|
| TR01 | Transfer of patent right |