CN108892134A - A kind of preparation method of composite graphite alkene Electric radiant Heating Film - Google Patents
A kind of preparation method of composite graphite alkene Electric radiant Heating Film Download PDFInfo
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- CN108892134A CN108892134A CN201810868281.0A CN201810868281A CN108892134A CN 108892134 A CN108892134 A CN 108892134A CN 201810868281 A CN201810868281 A CN 201810868281A CN 108892134 A CN108892134 A CN 108892134A
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 51
- 239000010439 graphite Substances 0.000 title claims abstract description 51
- 238000010438 heat treatment Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- -1 graphite alkene Chemical class 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 165
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 148
- 239000010408 film Substances 0.000 claims abstract description 76
- 239000006185 dispersion Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000010409 thin film Substances 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 12
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 36
- 239000011521 glass Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 28
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 12
- 238000005057 refrigeration Methods 0.000 claims description 12
- 235000010344 sodium nitrate Nutrition 0.000 claims description 12
- 239000004317 sodium nitrate Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000006059 cover glass Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 230000005496 eutectics Effects 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 210000004907 gland Anatomy 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 239000000523 sample Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 238000003490 calendering Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- 239000010410 layer Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- DECWYWSYTFTUAV-UHFFFAOYSA-N 1-methyl-2-propylimidazole Chemical compound CCCC1=NC=CN1C DECWYWSYTFTUAV-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 229910001120 nichrome Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HGGLDADJQQPKKC-UHFFFAOYSA-N 2-butyl-1-methylimidazole Chemical compound CCCCC1=NC=CN1C HGGLDADJQQPKKC-UHFFFAOYSA-N 0.000 description 1
- 229910001017 Alperm Inorganic materials 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- 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
-
- 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
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
Abstract
The invention discloses a kind of preparation methods of composite graphite alkene Electric radiant Heating Film, and the preparation method comprises the following steps：The first step prepares graphene oxide solution using improved Hummers method, and is washed to neutrality；Second step is frozen and dried；Third step, the preparation of graphene oxide dispersion；4th step, coating, plastic；5th step, is prepared graphene composite thin film；6th step, the reduction of graphene composite thin film obtain composite graphite alkene Electric radiant Heating Film；The preparation method of composite graphite alkene Electric radiant Heating Film of the invention, the combined oxidation graphene film prepared using the preparation method of composite graphite alkene Electric radiant Heating Film of the invention is after hydroiodic acid reduction, composite graphite alkene Electric radiant Heating Film is obtained after calendering technology, it is with good thermal conductivity and electric conductivity, and it is easy to operate, low in cost, energy consumption is smaller.
Description
Technical field
The present invention relates to a kind of preparation methods of composite graphite alkene Electric radiant Heating Film, belong to thermo electric material field.
Background technique
Electrical resistor heating element in common electric heating system generally uses metal foil, film coating, resistance wire, metal mesh etc.
Material；Most commonly used heating element is nichrome；However, still seeming in the following areas at present not for nichrome
Foot：The density of nichrome is greater than 8g/cm3, thickness has several millimeters when use；Resistivity low (~ 10–6Ω/m), however it remains
Electric heating conversion efficiency is low, and the rate of heat addition is small, and heating element does not have automatic constant-temperature and power compensation function, so that electric heating system structure
In place of the deficiencies of complexity, thermal inertia is big；Ferrum-chromium-aluminum is Alfer, and there are cold-shortnesses, 475 DEG C of brittleness and 1000 DEG C or more
High-temperature brittleness, the elevated temperature strength as caused by high-temperature brittleness is low, and to eventually lead to heating element service life short；Alloy it is solderable
Property it is very poor, hardly possible repair；Graphene（Graphene）Be one kind by carbon atom with sp2It is in honeycomb lattice that hybridized orbit, which forms hexangle type,
（honeycomb crystal lattice）The single layer flat film being arranged to make up, the two-dimentional material of only one carbon atom thickness
Material；The excellent electrical and thermal conductivity performance of graphene is well beyond metal, while graphene has the advantages that corrosion-and high-temp-resistant, and its
Good mechanical performance and lower density more allow it to have the potentiality in thermo electric material field substituted metal；Due to graphene
Large-scale processing is increasingly becoming reality, and graphene film applies substituted metal material in different fields.Chinese Patent Application No.：
201610690049.3 disclosing a kind of preparation method of composite graphite alkene Electric radiant Heating Film, this method comprises the following steps：（1）Preparation
Graphene oxide solution is mixed in reaction by 250g natural graphite and by the 5L nitration mixture that the 4.5L concentrated sulfuric acid and 0.5L concentrated phosphoric acid form
It is in kettle and uniform with automatically controlled magnetic stirrer, 500g potassium permanganate is slowly added in the case where being lower than 20 DEG C；Later, close
Envelope reaction kettle is simultaneously warming up to 85-90 DEG C of reaction 2-3 hours, and product is taken out from reaction kettle lower end, 40L solution is diluted to, is added
0.6L hydrogen peroxide obtains glassy yellow graphite oxide solution；Then, it is washed with acid and water alternating centrifugal, until pH value of solution=5-6, goes to clean
Matter ion；Finally, ultrasonic disperse graphite oxide, configures graphene oxide solution；（2）The above-mentioned oxygen for being 5-15mg/mL by concentration
Graphite aqueous solution stops in solidification liquid or liquid nitrogen after continuously and smoothly's extrusion in the preparation facilities exported with linear type
10-100 seconds, it is frozen into graphene oxide gel film, graphene oxide gel film is put into -10 ~ -15 DEG C of refrigerator and freezes 2-
It is rapidly frozen in 5h or liquid nitrogen；（3）Graphite oxide aerogel film after jelly is handled is sent into high temperature furnace and carries out high warm
Processing, processing mode are：400 DEG C first are warming up to 2-3 DEG C/min under atmosphere of inert gases, 0.5-1h is kept the temperature, then lazy
Property atmosphere under with 2-4 DEG C/min be warming up to 1300 DEG C, 1-4h is kept the temperature, then with 2-4 DEG C/min under atmosphere of inert gases
3000 DEG C are warming up to, 1-2h is kept the temperature, can be obtained the pure graphene aerogel film of continuous ultralight rule orientating；By aerogel film
High pressure compacting after, pressure 20-50MPa obtains composite graphite alkene Electric radiant Heating Film, using the above method can it is pollution-free, be able to batch
Production prepares graphene, and graphene film has fine toughness, can arbitrarily bend and keep good electric conductivity, have high
Machinability is conducive to the various shape adapted to, the demand of various applications.But the preparation side of above-mentioned composite graphite alkene Electric radiant Heating Film
Its step of method（3）In the reduction of graphite oxide aerogel film in, need under the protection of inert gas, by high temperature by oxygen
The reduction of graphite alkene, although this method can complete restoring operation, whole operation carries out comparatively laborious, high temperature furnace
Heating need the regular hour, and whole process needs the protection of inert gas, in addition reduction the time it takes, not only
Time-consuming, and higher cost；Therefore, in order to solve problem above, it would be highly desirable to study a kind of system of new composite graphite alkene Electric radiant Heating Film
Preparation Method.
Summary of the invention
To solve the above problems, the invention proposes a kind of preparation method of composite graphite alkene Electric radiant Heating Film, it is easy to operate, at
This is cheap, and energy consumption is smaller.
The preparation method of composite graphite alkene Electric radiant Heating Film of the invention, the preparation method comprises the following steps：
The first step prepares graphene oxide solution using improved Hummers method, and is washed to neutrality；
1）0.5g sodium nitrate powder and the concentrated sulfuric acid of 70ml are weighed, is put into the beaker of 500ml, beaker is moved into mixture of ice and water
In, 30min is stirred under the conditions of 0 DEG C of ice-water bath, until sodium nitrate is completely dissolved；
2）1g spherical graphite is weighed, is added slowly in beaker, continues to stir 30min after all adding, until graphite mixes
Uniformly；
3) 3gKMnO is weighed4, it is slowly added in beaker with the speed of every 10 minutes addition 1g, whole process continues 30min, needs
It is to be noted that this process is slow as far as possible, prevent due to be added it is too fast cause local reaction excessively, reaction temperature increase, thus shadow
Ring yield；Temperature is controlled in whole process and is no more than 10 DEG C, to KMnO4After being all added, high-speed stirred 2h, solution is gradually at this time
It is changed into blackish green；
4）Beaker is moved into 35 DEG C of water-baths, continues to stir 2h；
5）100ml deionized water is added into beaker, when temperature reaches 80 DEG C, beaker is moved into 85 DEG C of water-bath and be stirred
30min；
6）Above-mentioned mixed liquor is moved into the beaker of 1L, is diluted to 500ml with 60 DEG C of deionized water, adds 60ml5wt%'s
Hydrogen peroxide solution until no longer generating a large amount of bubbles, continues to stir 20 minutes until glassy yellow is presented in solution；
7）Above-mentioned mixed liquor is staggeredly washed with 10% hydrochloric acid solution and deionized water respectively, repeatedly operation 4 ~ 5 times, directly
It is in neutrality to solution；
Second step is frozen and dried,
1）The graphene oxide solution being in neutrality prepared in the first step is packed into material disc by precooling after diluting, and is opened
Vacuum-refrigerator first carries out precooling to the refrigeration storehouse of vacuum-refrigerator；Then material disc is put into the pre-freeze frame in refrigeration storehouse, it will
Chiller probe comes into full contact with material, and then freezing frame is put into cold-trap, cover pre-freeze lid, when pre-freeze to material each section all
After dropping to material eutectic point or less, then 1 ~ 1.5h is maintained, pre-freeze terminates；
2）It is dry, the good material of pre-freeze is moved on on gland drier, then drier is placed on cold-trap, organic glass on cover
Glass cover opens vacuum meter, and carries out vacuum pumping to cold-trap with vacuum pump after screwing discharging valve, be less than internal vacuum
20Pa, 2 ~ 5h of drying time obtain fluffy graphene oxide solid；
Third step, the preparation of graphene oxide dispersion,
Graphene oxide solid after weighing drying, is added to the water, and prepares and obtains the graphene oxide that mass fraction is 1wt%
Solution can instill a little ethanol solution to enhance dispersibility；Then mixed liquor is subjected to emulsification pretreatment operation, so that cluster
Tissue can be dispersed under the action of high speed shear, obtain dispersion liquid more evenly；Emulsification pretreatment speed be 1100 ~
1200r/min, time are 3 ~ 7min；Finally dispersion liquid is moved into and carries out ultrasound procedure 1h in Ultrasound Instrument, obtains graphene oxide
Dispersion liquid；
4th step, coating, plastic,
By the concentration of graphene oxide dispersion, by the means such as being concentrated or diluting, adjusts and arrive 10mg/ml；Glass base will be passed through
It is coated in the graphene oxide dispersion of bottom immersion 10mg/ml, then will have the glass base of graphene oxide dispersion
Plastic in the solidification liquid of 0.1mol/ml is immersed at bottom；
5th step, is prepared graphene composite thin film,
Substrate is taken out, and substrate is put in a drying box into drying, controls 50 ~ 70 DEG C of drying temperature, by the drying of 6 ~ 8h,
One layer of graphene composite thin film is covered in substrate of glass；Film is stripped down from substrate of glass, obtains oxidation stone
Black alkene laminated film；
6th step, the reduction of graphene composite thin film obtain composite graphite alkene Electric radiant Heating Film,
It evaporates steam at 80 DEG C using hydroiodic acid to restore above-mentioned graphene composite thin film, after for 24 hours
Obtain graphene composite film；Obtained graphene composite film is rolled by calender finally, is obtained of the invention compound
Graphene Electric radiant Heating Film, by the calendering of calender, so that graphene composite film has good flexibility, ductility and orientation
Property.
As preferred embodiment, in the preparation of the graphene oxide dispersion of the third step, it is to mass fraction
Ethanol solution is added dropwise in the graphene oxide solution of 1wt%, enhances the dispersibility of dispersion liquid.
Further, the solidification liquid in the 4th step is small molecule compound comprising CaCl2, 1- butyl -3- methyl
Imidazoles L lactate, chlorination 1- amine propyl -3- methylimidazole or 1,8- octamethylenediamine, due to oxygen-containing on graphene oxide layer surface
Acid group has negative electrical charge, CaCl2With cation contained in ionic liquid, can shield it is mutually exclusive between negative electrical charge,
So that film plastic；1- butyl -3- methylimidazole L lactate, chlorination 1- amine propyl -3- methylimidazole and 1,8- octamethylenediamine ion
At least contain-a NH in liquid2Group can form amido bond, oxidation reinforced stone with the-COOH in graphene oxide layer
The crosslinking of black alkene lamella.
The present invention compared with prior art, the preparation method of composite graphite alkene Electric radiant Heating Film of the invention, using the present invention
Composite graphite alkene Electric radiant Heating Film preparation method preparation combined oxidation graphene film hydroiodic acid reduction after, by calendering
Composite graphite alkene Electric radiant Heating Film is obtained after technique, with good thermal conductivity and electric conductivity, and easy to operate, low in cost, energy
It consumes smaller.
Detailed description of the invention
Fig. 1 is raw material graphene oxide of the invention, CaCl2, 1- butyl -3- methylimidazole L lactate, chlorination 1- amine third
Base -3- methylimidazole and 1,8- octamethylenediamine structural formula schematic diagram；
Wherein, scheme（a）For the structural formula of raw material graphene oxide, figure（b）For CaCl2Structural formula, figure（c）For 1-
The structural formula of butyl -3- methylimidazole L lactate, figure（d）For the molecular formula knot of chlorination 1- amine propyl -3- methylimidazole
Structure, figure（e）For the structural formula of 1,8- octamethylenediamine.
Specific embodiment
Embodiment 1：
The preparation method of composite graphite alkene Electric radiant Heating Film of the invention, the preparation method comprises the following steps：
The first step prepares graphene oxide solution using improved Hummers method, and is washed to neutrality；
1）0.5g sodium nitrate powder and the concentrated sulfuric acid of 70ml are weighed, is put into the beaker of 500ml, beaker is moved into mixture of ice and water
In, 30min is stirred under the conditions of 0 DEG C of ice-water bath, until sodium nitrate is completely dissolved；
2）1g spherical graphite is weighed, is added slowly in beaker, continues to stir 30min after all adding, until graphite mixes
Uniformly；
3) 3gKMnO is weighed4, it is slowly added in beaker with the speed of every 10 minutes addition 1g, whole process continues 30min；Entirely
Control temperature is no more than 10 DEG C in the process, to KMnO4After being all added, high-speed stirred 2h, solution is gradually converted into blackish green at this time
Color；
4）Beaker is moved into 35 DEG C of water-baths, continues to stir 2h；
5）100ml deionized water is added into beaker, when temperature reaches 80 DEG C, beaker is moved into 85 DEG C of water-bath and be stirred
30min；
6）Above-mentioned mixed liquor is moved into the beaker of 1L, is diluted to 500ml with 60 DEG C of deionized water, adds 60ml5wt%'s
Hydrogen peroxide solution until no longer generating a large amount of bubbles, continues to stir 20 minutes until glassy yellow is presented in solution；
7）Above-mentioned mixed liquor is staggeredly washed with 10% hydrochloric acid solution and deionized water respectively, repeatedly operation 4 ~ 5 times, directly
It is in neutrality to solution；
Second step is frozen and dried,
1）The graphene oxide solution being in neutrality prepared in the first step is packed into material disc by precooling after diluting, and is opened
Vacuum-refrigerator first carries out precooling to the refrigeration storehouse of vacuum-refrigerator；Then material disc is put into the pre-freeze frame in refrigeration storehouse, it will
Chiller probe comes into full contact with material, and then freezing frame is put into cold-trap, cover pre-freeze lid, when pre-freeze to material each section all
After dropping to material eutectic point or less, then 1h is maintained, pre-freeze terminates；
2）It is dry, the good material of pre-freeze is moved on on gland drier, then drier is placed on cold-trap, organic glass on cover
Glass cover opens vacuum meter, and carries out vacuum pumping to cold-trap with vacuum pump after screwing discharging valve, be less than internal vacuum
20Pa, drying time 3h obtain fluffy graphene oxide solid；
Third step, the preparation of graphene oxide dispersion,
Graphene oxide solid after weighing drying, is added to the water, and prepares and obtains the graphene oxide that mass fraction is 1wt%
Solution, and ethanol solution is added dropwise to the graphene oxide solution that mass fraction is 1wt%, enhance the dispersibility of dispersion liquid；Then will
Mixed liquor carries out emulsification pretreatment operation, and the tissue of cluster is dispersed under the action of high speed shear, obtains more
Even dispersion liquid；Emulsification pretreatment speed is 1200r/min, time 3min；Finally dispersion liquid is moved into Ultrasound Instrument and is surpassed
Sound operates 1h, obtains graphene oxide dispersion；
4th step, coating, plastic,
By the concentration of graphene oxide dispersion, by the means such as being concentrated or diluting, adjusts and arrive 10mg/ml；Glass base will be passed through
It is coated in the graphene oxide dispersion of bottom immersion 10mg/ml, then will have the glass base of graphene oxide dispersion
The CaCl of bottom immersion 0.1mol/ml2Middle plastic；
5th step, is prepared graphene composite thin film,
Substrate is taken out, and substrate is put in a drying box into drying, 60 DEG C of drying temperature are controlled, by the drying of 8h, in glass
One layer of graphene composite thin film is covered in substrate；Film is stripped down from substrate of glass, obtains graphene oxide
Laminated film；
6th step, the reduction of graphene composite thin film obtain composite graphite alkene Electric radiant Heating Film,
It evaporates steam at 80 DEG C using hydroiodic acid to restore above-mentioned graphene composite thin film, after for 24 hours
Obtain graphene composite film；Obtained graphene composite film is rolled by calender finally, is obtained of the invention compound
Graphene Electric radiant Heating Film, by the calendering of calender, so that graphene composite film has good flexibility, ductility and orientation
Property.
Embodiment 2：
The preparation method of composite graphite alkene Electric radiant Heating Film of the invention, the preparation method comprises the following steps：
The first step prepares graphene oxide solution using improved Hummers method, and is washed to neutrality；
1）0.5g sodium nitrate powder and the concentrated sulfuric acid of 70ml are weighed, is put into the beaker of 500ml, beaker is moved into mixture of ice and water
In, 30min is stirred under the conditions of 0 DEG C of ice-water bath, until sodium nitrate is completely dissolved；
2）1g spherical graphite is weighed, is added slowly in beaker, continues to stir 30min after all adding, until graphite mixes
Uniformly；
3) 3gKMnO is weighed4, it is slowly added in beaker with the speed of every 10 minutes addition 1g, whole process continues 30min；Entirely
Control temperature is no more than 10 DEG C in the process, to KMnO4After being all added, high-speed stirred 2h, solution is gradually converted into blackish green at this time
Color；
4）Beaker is moved into 35 DEG C of water-baths, continues to stir 2h；
5）100ml deionized water is added into beaker, when temperature reaches 80 DEG C, beaker is moved into 85 DEG C of water-bath and be stirred
30min；
6）Above-mentioned mixed liquor is moved into the beaker of 1L, is diluted to 500ml with 60 DEG C of deionized water, adds 60ml5wt%'s
Hydrogen peroxide solution until no longer generating a large amount of bubbles, continues to stir 20 minutes until glassy yellow is presented in solution；
7）Above-mentioned mixed liquor is staggeredly washed with 10% hydrochloric acid solution and deionized water respectively, repeatedly operation 4 ~ 5 times, directly
It is in neutrality to solution；
Second step is frozen and dried,
1）The graphene oxide solution being in neutrality prepared in the first step is packed into material disc by precooling after diluting, and is opened
Vacuum-refrigerator first carries out precooling to the refrigeration storehouse of vacuum-refrigerator；Then material disc is put into the pre-freeze frame in refrigeration storehouse, it will
Chiller probe comes into full contact with material, and then freezing frame is put into cold-trap, cover pre-freeze lid, when pre-freeze to material each section all
After dropping to material eutectic point or less, then 1.5h is maintained, pre-freeze terminates；
2）It is dry, the good material of pre-freeze is moved on on gland drier, then drier is placed on cold-trap, organic glass on cover
Glass cover opens vacuum meter, and carries out vacuum pumping to cold-trap with vacuum pump after screwing discharging valve, be less than internal vacuum
20Pa, drying time 3h obtain fluffy graphene oxide solid；
Third step, the preparation of graphene oxide dispersion,
Graphene oxide solid after weighing drying, is added to the water, and prepares and obtains the graphene oxide that mass fraction is 1wt%
Solution, and ethanol solution is added dropwise to the graphene oxide solution that mass fraction is 1wt%, enhance the dispersibility of dispersion liquid；Then will
Mixed liquor carries out emulsification pretreatment operation, and the tissue of cluster is dispersed under the action of high speed shear, obtains more
Even dispersion liquid；Emulsification pretreatment speed is 1100r/min, time 6min；Finally dispersion liquid is moved into Ultrasound Instrument and is surpassed
Sound operates 1h, obtains graphene oxide dispersion；
4th step, coating, plastic,
By the concentration of graphene oxide dispersion, by the means such as being concentrated or diluting, adjusts and arrive 10mg/ml；Glass base will be passed through
It is coated in the graphene oxide dispersion of bottom immersion 10mg/ml, then will have the glass base of graphene oxide dispersion
Plastic in the 1- butyl -3- methylimidazole L lactate of 0.1mol/ml is immersed at bottom；
5th step, is prepared graphene composite thin film,
Substrate is taken out, and substrate is put in a drying box into drying, 55 DEG C of drying temperature are controlled, by the drying of 8h, in glass
One layer of graphene composite thin film is covered in substrate；Film is stripped down from substrate of glass, obtains graphene oxide
Laminated film；
6th step, the reduction of graphene composite thin film obtain composite graphite alkene Electric radiant Heating Film,
It evaporates steam at 80 DEG C using hydroiodic acid to restore above-mentioned graphene composite thin film, after for 24 hours
Obtain graphene composite film；Obtained graphene composite film is rolled by calender finally, is obtained of the invention compound
Graphene Electric radiant Heating Film, by the calendering of calender, so that graphene composite film has good flexibility, ductility and orientation
Property.
Embodiment 3：
The preparation method of composite graphite alkene Electric radiant Heating Film of the invention, the preparation method comprises the following steps：
The first step prepares graphene oxide solution using improved Hummers method, and is washed to neutrality；
1）0.5g sodium nitrate powder and the concentrated sulfuric acid of 70ml are weighed, is put into the beaker of 500ml, beaker is moved into mixture of ice and water
In, 30min is stirred under the conditions of 0 DEG C of ice-water bath, until sodium nitrate is completely dissolved；
2）1g spherical graphite is weighed, is added slowly in beaker, continues to stir 30min after all adding, until graphite mixes
Uniformly；
3) 3gKMnO is weighed4, it is slowly added in beaker with the speed of every 10 minutes addition 1g, whole process continues 30min；Entirely
Control temperature is no more than 10 DEG C in the process, to KMnO4After being all added, high-speed stirred 2h, solution is gradually converted into blackish green at this time
Color；
4）Beaker is moved into 35 DEG C of water-baths, continues to stir 2h；
5）100ml deionized water is added into beaker, when temperature reaches 80 DEG C, beaker is moved into 85 DEG C of water-bath and be stirred
30min；
6）Above-mentioned mixed liquor is moved into the beaker of 1L, is diluted to 500ml with 60 DEG C of deionized water, adds 60ml5wt%'s
Hydrogen peroxide solution until no longer generating a large amount of bubbles, continues to stir 20 minutes until glassy yellow is presented in solution；
7）Above-mentioned mixed liquor is staggeredly washed with 10% hydrochloric acid solution and deionized water respectively, repeatedly operation 4 ~ 5 times, directly
It is in neutrality to solution；
Second step is frozen and dried,
1）The graphene oxide solution being in neutrality prepared in the first step is packed into material disc by precooling after diluting, and is opened
Vacuum-refrigerator first carries out precooling to the refrigeration storehouse of vacuum-refrigerator；Then material disc is put into the pre-freeze frame in refrigeration storehouse, it will
Chiller probe comes into full contact with material, and then freezing frame is put into cold-trap, cover pre-freeze lid, when pre-freeze to material each section all
After dropping to material eutectic point or less, then 1h is maintained, pre-freeze terminates；
2）It is dry, the good material of pre-freeze is moved on on gland drier, then drier is placed on cold-trap, organic glass on cover
Glass cover opens vacuum meter, and carries out vacuum pumping to cold-trap with vacuum pump after screwing discharging valve, be less than internal vacuum
20Pa, 2 ~ 5h of drying time obtain fluffy graphene oxide solid；
Third step, the preparation of graphene oxide dispersion,
Graphene oxide solid after weighing drying, is added to the water, and prepares and obtains the graphene oxide that mass fraction is 1wt%
Solution, and ethanol solution is added dropwise to the graphene oxide solution that mass fraction is 1wt%, enhance the dispersibility of dispersion liquid；Then will
Mixed liquor carries out emulsification pretreatment operation, and the tissue of cluster is dispersed under the action of high speed shear, obtains more
Even dispersion liquid；Emulsification pretreatment speed is 1200r/min, time 4min；Finally dispersion liquid is moved into Ultrasound Instrument and is surpassed
Sound operates 1h, obtains graphene oxide dispersion；
4th step, coating, plastic,
By the concentration of graphene oxide dispersion, by the means such as being concentrated or diluting, adjusts and arrive 10mg/ml；Glass base will be passed through
It is coated in the graphene oxide dispersion of bottom immersion 10mg/ml, then will have the glass base of graphene oxide dispersion
Plastic in the chlorination 1- amine propyl -3- methylimidazole of 0.1mol/ml is immersed at bottom；
5th step, is prepared graphene composite thin film,
Substrate is taken out, and substrate is put in a drying box into drying, 60 DEG C of drying temperature are controlled, by the drying of 8h, in glass
One layer of graphene composite thin film is covered in substrate；Film is stripped down from substrate of glass, obtains graphene oxide
Laminated film；
6th step, the reduction of graphene composite thin film obtain composite graphite alkene Electric radiant Heating Film,
It evaporates steam at 80 DEG C using hydroiodic acid to restore above-mentioned graphene composite thin film, after for 24 hours
Obtain graphene composite film；Obtained graphene composite film is rolled by calender finally, is obtained of the invention compound
Graphene Electric radiant Heating Film, by the calendering of calender, so that graphene composite film has good flexibility, ductility and orientation
Property.
Embodiment 4：
The preparation method of composite graphite alkene Electric radiant Heating Film of the invention, the preparation method comprises the following steps：
The first step prepares graphene oxide solution using improved Hummers method, and is washed to neutrality；
1）0.5g sodium nitrate powder and the concentrated sulfuric acid of 70ml are weighed, is put into the beaker of 500ml, beaker is moved into mixture of ice and water
In, 30min is stirred under the conditions of 0 DEG C of ice-water bath, until sodium nitrate is completely dissolved；
2）1g spherical graphite is weighed, is added slowly in beaker, continues to stir 30min after all adding, until graphite mixes
Uniformly；
3) 3gKMnO is weighed4, it is slowly added in beaker with the speed of every 10 minutes addition 1g, whole process continues 30min；Entirely
Control temperature is no more than 10 DEG C in the process, to KMnO4After being all added, high-speed stirred 2h, solution is gradually converted into blackish green at this time
Color；
4）Beaker is moved into 35 DEG C of water-baths, continues to stir 2h；
5）100ml deionized water is added into beaker, when temperature reaches 80 DEG C, beaker is moved into 85 DEG C of water-bath and be stirred
30min；
6）Above-mentioned mixed liquor is moved into the beaker of 1L, is diluted to 500ml with 60 DEG C of deionized water, adds 60ml5wt%'s
Hydrogen peroxide solution until no longer generating a large amount of bubbles, continues to stir 20 minutes until glassy yellow is presented in solution；
7）Above-mentioned mixed liquor is staggeredly washed with 10% hydrochloric acid solution and deionized water respectively, repeatedly operation 4 ~ 5 times, directly
It is in neutrality to solution；
Second step is frozen and dried,
1）The graphene oxide solution being in neutrality prepared in the first step is packed into material disc by precooling after diluting, and is opened
Vacuum-refrigerator first carries out precooling to the refrigeration storehouse of vacuum-refrigerator；Then material disc is put into the pre-freeze frame in refrigeration storehouse, it will
Chiller probe comes into full contact with material, and then freezing frame is put into cold-trap, cover pre-freeze lid, when pre-freeze to material each section all
After dropping to material eutectic point or less, then 1h is maintained, pre-freeze terminates；
2）It is dry, the good material of pre-freeze is moved on on gland drier, then drier is placed on cold-trap, organic glass on cover
Glass cover opens vacuum meter, and carries out vacuum pumping to cold-trap with vacuum pump after screwing discharging valve, be less than internal vacuum
20Pa, drying time 3h obtain fluffy graphene oxide solid；
Third step, the preparation of graphene oxide dispersion,
Graphene oxide solid after weighing drying, is added to the water, and prepares and obtains the graphene oxide that mass fraction is 1wt%
Solution, and ethanol solution is added dropwise to the graphene oxide solution that mass fraction is 1wt%, enhance the dispersibility of dispersion liquid；Then will
Mixed liquor carries out emulsification pretreatment operation, and the tissue of cluster is dispersed under the action of high speed shear, obtains more
Even dispersion liquid；Emulsification pretreatment speed is 1100r/min, time 5min；Finally dispersion liquid is moved into Ultrasound Instrument and is surpassed
Sound operates 1h, obtains graphene oxide dispersion；
4th step, coating, plastic,
By the concentration of graphene oxide dispersion, by the means such as being concentrated or diluting, adjusts and arrive 10mg/ml；Glass base will be passed through
It is coated in the graphene oxide dispersion of bottom immersion 10mg/ml, then will have the glass base of graphene oxide dispersion
Plastic in 1, the 8- octamethylenediamine of 0.1mol/ml is immersed at bottom；
5th step, is prepared graphene composite thin film,
Substrate is taken out, and substrate is put in a drying box into drying, 70 DEG C of drying temperature are controlled, by the drying of 7h, in glass
One layer of graphene composite thin film is covered in substrate；Film is stripped down from substrate of glass, obtains graphene oxide
Laminated film；
6th step, the reduction of graphene composite thin film obtain composite graphite alkene Electric radiant Heating Film,
It evaporates steam at 80 DEG C using hydroiodic acid to restore above-mentioned graphene composite thin film, after for 24 hours
Obtain graphene composite film；Obtained graphene composite film is rolled by calender finally, is obtained of the invention compound
Graphene Electric radiant Heating Film, by the calendering of calender, so that graphene composite film has good flexibility, ductility and orientation
Property.
The preparation method of composite graphite alkene Electric radiant Heating Film of the invention, as shown in Figure 1, due on graphene oxide layer surface
Oxygen-containing acid group has negative electrical charge, CaCl2With cation contained in ionic liquid, the mutual row between negative electrical charge can be shielded
Reprimand, so that film plastic；1- butyl -3- methylimidazole L lactate, chlorination 1- amine propyl -3- methylimidazole and 1,8- octamethylenediamine
At least contain-a NH in ionic liquid2Group can form amido bond with the-COOH in graphene oxide layer, reinforce oxygen
The crosslinking of graphite alkene lamella；The calcium ion in calcium chloride in embodiment 1 enters graphene oxide interlayer, so that oxidation stone
The electrostatic repulsion of black alkene piece interlayer weakens, and orientation is reinforced, and then forms colloid not soluble in water；Embodiment 2 uses 1- butyl-
3- methylimidazole L lactate is as solidification liquid, and reaction process is similar to Example 1, but in example 2,1- butyl -3- first
Cationic size is greater than calcium ion in its ionic liquid of base imidazoles L lactate, so graphene oxide layer takes original
Tropism upper piece interlamellar spacing increases；Due to having-a NH in the chlorination 1- amine propyl -3- methylimidazole in embodiment 32, so
Its cation can form amido bond with-COOH, to further increase its piece interlamellar spacing when entering graphene oxide layer；
1,8- octamethylenediamine in embodiment 4 contain there are two-NH2, and its carbochain is longer, it can be as bridge by two graphene sheet layers
Together using covalent bond institute, to further widen the interlamellar spacing of graphene oxide.
Above-described embodiment is only better embodiment of the invention, therefore all according to structure described in present patent application range
It makes, the equivalent change or modification that feature and principle are done, is included in the scope of the patent application of the present invention.
Claims (3)
1. a kind of preparation method of composite graphite alkene Electric radiant Heating Film, which is characterized in that the preparation method comprises the following steps：
The first step prepares graphene oxide solution using improved Hummers method, and is washed to neutrality；
1）0.5g sodium nitrate powder and the concentrated sulfuric acid of 70ml are weighed, is put into the beaker of 500ml, beaker is moved into mixture of ice and water
In, 30min is stirred under the conditions of 0 DEG C of ice-water bath, until sodium nitrate is completely dissolved；
2）1g spherical graphite is weighed, is added slowly in beaker, continues to stir 30min after all adding, until graphite mixes
Uniformly；
3) 3gKMnO is weighed4, it is slowly added in beaker with the speed of every 10 minutes addition 1g, whole process continues 30min；Entirely
Control temperature is no more than 10 DEG C in the process, to KMnO4After being all added, high-speed stirred 2h, solution is gradually converted into blackish green at this time
Color；
4）Beaker is moved into 35 DEG C of water-baths, continues to stir 2h；
5）100ml deionized water is added into beaker, when temperature reaches 80 DEG C, beaker is moved into 85 DEG C of water-bath and be stirred
30min；
6）Above-mentioned mixed liquor is moved into the beaker of 1L, is diluted to 500ml with 60 DEG C of deionized water, adds 60ml5wt%'s
Hydrogen peroxide solution until no longer generating a large amount of bubbles, continues to stir 20 minutes until glassy yellow is presented in solution；
7）Above-mentioned mixed liquor is staggeredly washed with 10% hydrochloric acid solution and deionized water respectively, repeatedly operation 4 ~ 5 times, directly
It is in neutrality to solution；
Second step is frozen and dried,
1）The graphene oxide solution being in neutrality prepared in the first step is packed into material disc by precooling after diluting, and is opened
Vacuum-refrigerator first carries out precooling to the refrigeration storehouse of vacuum-refrigerator；Then material disc is put into the pre-freeze frame in refrigeration storehouse, it will
Chiller probe comes into full contact with material, and then freezing frame is put into cold-trap, cover pre-freeze lid, when pre-freeze to material each section all
After dropping to material eutectic point or less, then 1 ~ 1.5h is maintained, pre-freeze terminates；
2）It is dry, the good material of pre-freeze is moved on on gland drier, then drier is placed on cold-trap, organic glass on cover
Glass cover opens vacuum meter, and carries out vacuum pumping to cold-trap with vacuum pump after screwing discharging valve, be less than internal vacuum
20Pa, 2 ~ 5h of drying time obtain fluffy graphene oxide solid；
Third step, the preparation of graphene oxide dispersion,
Graphene oxide solid after weighing drying, is added to the water, and prepares and obtains the graphene oxide that mass fraction is 1wt%
Solution；Then mixed liquor is subjected to emulsification pretreatment operation, the tissue of cluster is dispersed under the action of high speed shear
It opens, obtains dispersion liquid more evenly；Emulsification pretreatment speed is 1100 ~ 1200r/min, and the time is 3 ~ 7min；Finally by dispersion liquid
It moves into and carries out ultrasound procedure 1h in Ultrasound Instrument, obtain graphene oxide dispersion；
4th step, coating, plastic,
By the concentration of graphene oxide dispersion, by the means such as being concentrated or diluting, adjusts and arrive 10mg/ml；Glass base will be passed through
It is coated in the graphene oxide dispersion of bottom immersion 10mg/ml, then will have the glass base of graphene oxide dispersion
Plastic in the solidification liquid of 0.1mol/ml is immersed at bottom；
5th step, is prepared graphene composite thin film,
Substrate is taken out, and substrate is put in a drying box into drying, controls 50 ~ 70 DEG C of drying temperature, by the drying of 6 ~ 8h,
One layer of graphene composite thin film is covered in substrate of glass；Film is stripped down from substrate of glass, obtains oxidation stone
Black alkene laminated film；
6th step, the reduction of graphene composite thin film obtain composite graphite alkene Electric radiant Heating Film,
It evaporates steam at 80 DEG C using hydroiodic acid to restore above-mentioned graphene composite thin film, after for 24 hours
Obtain graphene composite film；Obtained graphene composite film is rolled by calender finally, is obtained of the invention compound
Graphene Electric radiant Heating Film.
2. the preparation method of composite graphite alkene Electric radiant Heating Film according to claim 1, which is characterized in that the oxygen of the third step
In the preparation of graphite alkene dispersion liquid, ethanol solution is added dropwise to the graphene oxide solution that mass fraction is 1wt%.
3. the preparation method of composite graphite alkene Electric radiant Heating Film according to claim 1, which is characterized in that in the 4th step
Solidification liquid is small molecule compound comprising CaCl2, 1- butyl -3- methylimidazole L lactate, chlorination 1- amine propyl -3- methyl
Imidazoles or 1,8- octamethylenediamine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111743192A (en) * | 2020-07-10 | 2020-10-09 | 湖北中烟工业有限责任公司 | Preparation method of geraniol-graphene oxide slow-release heat-conducting composite material for cigarettes |
| CN112299404A (en) * | 2020-09-21 | 2021-02-02 | 宁波华丰包装有限公司 | Method for preparing graphene oxide film in batch and graphene oxide film prepared by method |
| WO2021115669A1 (en) | 2019-12-09 | 2021-06-17 | Robert Bosch Gmbh | Electrical conductor made of graphene and/or carbon nanotubes having coated joints |
| CN113817288A (en) * | 2021-09-04 | 2021-12-21 | 高祥 | Heat-conducting engineering plastic and preparation method thereof |
| DE102021210974A1 (en) | 2021-09-30 | 2023-03-30 | Robert Bosch Gesellschaft mit beschränkter Haftung | Electrical machine and method for inserting at least one electrical conductor assembly into at least one slot of a stator or rotor for an electrical machine |
| DE102022203207A1 (en) | 2022-03-31 | 2023-10-05 | Robert Bosch Gesellschaft mit beschränkter Haftung | Process for producing a graphene film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
| CN103387225A (en) * | 2012-11-21 | 2013-11-13 | 厦门凯纳石墨烯技术有限公司 | Heat-conducting graphite membrane and preparation method |
| CN104118867A (en) * | 2014-07-07 | 2014-10-29 | 苏州世优佳电子科技有限公司 | Preparation method of graphite oxide |
| CN106241776A (en) * | 2016-07-13 | 2016-12-21 | 南京邮电大学 | A kind of preparation method of the graphene composite thin film of LBL self-assembly |
| 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 |
| WO2017201987A1 (en) * | 2016-05-24 | 2017-11-30 | 福州大学 | Antistatic composite nanomaterial film and preparation method thereof |
| WO2018004099A1 (en) * | 2016-06-27 | 2018-01-04 | 재단법인차세대융합기술연구원 | Graphene oxide/carbon nanotube composite fiber having heterojunction structure, and method for manufacturing graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber |
-
2018
- 2018-08-02 CN CN201810868281.0A patent/CN108892134A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
| CN103387225A (en) * | 2012-11-21 | 2013-11-13 | 厦门凯纳石墨烯技术有限公司 | Heat-conducting graphite membrane and preparation method |
| CN104118867A (en) * | 2014-07-07 | 2014-10-29 | 苏州世优佳电子科技有限公司 | Preparation method of graphite oxide |
| WO2017201987A1 (en) * | 2016-05-24 | 2017-11-30 | 福州大学 | Antistatic composite nanomaterial film and preparation method thereof |
| WO2018004099A1 (en) * | 2016-06-27 | 2018-01-04 | 재단법인차세대융합기술연구원 | Graphene oxide/carbon nanotube composite fiber having heterojunction structure, and method for manufacturing graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber |
| CN106241776A (en) * | 2016-07-13 | 2016-12-21 | 南京邮电大学 | A kind of preparation method of the graphene composite thin film of LBL self-assembly |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 周晓东 等: "高速剪切辅助氧化还原法制备石墨烯", 《材料导报》 * |
| 申佳欣: "石墨烯薄膜的制备工艺及其应用", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021115669A1 (en) | 2019-12-09 | 2021-06-17 | Robert Bosch Gmbh | Electrical conductor made of graphene and/or carbon nanotubes having coated joints |
| US11875913B2 (en) | 2019-12-09 | 2024-01-16 | Robert Bosch Gmbh | Electrical conductor made of graphene and/or carbon nanotubes having coated joints |
| CN111743192A (en) * | 2020-07-10 | 2020-10-09 | 湖北中烟工业有限责任公司 | Preparation method of geraniol-graphene oxide slow-release heat-conducting composite material for cigarettes |
| CN111743192B (en) * | 2020-07-10 | 2022-05-17 | 湖北中烟工业有限责任公司 | Preparation method of geraniol-graphene oxide slow-release heat-conducting composite material for cigarettes |
| CN112299404A (en) * | 2020-09-21 | 2021-02-02 | 宁波华丰包装有限公司 | Method for preparing graphene oxide film in batch and graphene oxide film prepared by method |
| CN113817288A (en) * | 2021-09-04 | 2021-12-21 | 高祥 | Heat-conducting engineering plastic and preparation method thereof |
| CN113817288B (en) * | 2021-09-04 | 2023-12-15 | 苏州和庚丽塑胶科技有限公司 | Heat-conducting engineering plastic and preparation method thereof |
| DE102021210974A1 (en) | 2021-09-30 | 2023-03-30 | Robert Bosch Gesellschaft mit beschränkter Haftung | Electrical machine and method for inserting at least one electrical conductor assembly into at least one slot of a stator or rotor for an electrical machine |
| WO2023052116A1 (en) | 2021-09-30 | 2023-04-06 | Robert Bosch Gmbh | Electric machine and method for placing at least one electrical composite conductor into at least one groove of a stator or rotor for an electric machine |
| DE102022203207A1 (en) | 2022-03-31 | 2023-10-05 | Robert Bosch Gesellschaft mit beschränkter Haftung | Process for producing a graphene film |
| WO2023186456A1 (en) | 2022-03-31 | 2023-10-05 | Robert Bosch Gmbh | Method for producing a graphene film |
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