CN115571873A - Impurity removal method for reducing graphene oxide film by using hydrogen halide - Google Patents
Impurity removal method for reducing graphene oxide film by using hydrogen halide Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 256
- 229910000039 hydrogen halide Inorganic materials 0.000 title claims abstract description 93
- 239000012433 hydrogen halide Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000012535 impurity Substances 0.000 title claims abstract description 59
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 84
- 150000002367 halogens Chemical class 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000002791 soaking Methods 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims description 21
- 238000003958 fumigation Methods 0.000 claims description 19
- 239000011229 interlayer Substances 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 description 68
- 230000009467 reduction Effects 0.000 description 52
- 239000010410 layer Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 23
- 239000003638 chemical reducing agent Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002932 luster Substances 0.000 description 6
- 238000004451 qualitative analysis Methods 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000013473 artificial intelligence Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- -1 halogen hydride Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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Classifications
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- 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
- C01B32/194—After-treatment
- C01B32/196—Purification
-
- 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
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- Chemical & Material Sciences (AREA)
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- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention provides an impurity removal method for reducing a graphene oxide film by using hydrogen halide. The impurity removal method for the hydrogen halide reduced graphene oxide film comprises the steps of acting hot water on the hydrogen halide reduced graphene oxide film in a fumigating or multiple soaking mode, enabling water molecules to enter the layers of graphene oxide, extruding halogen elements out of the layers of the graphene oxide film, fumigating or multiple soaking for less than 10 hours, and enabling the content of the halogen elements in the graphene oxide film to be less than 0.1%. The impurity removal method provided by the invention can rapidly remove halogen elements between graphene oxide film layers in a short time, has high impurity removal efficiency, and can reduce the content of the halogen elements to less than 0.1%.
Description
The application is filed in 2019, 05 and 30, and has the application number of 201910461612.3, and the invention name of a divisional application of a method for removing impurities from a hydrogen halide reduced graphene oxide film, a graphene heat-conducting film and a preparation method thereof.
Technical Field
The invention relates to a reduction process of a graphene oxide heat-conducting film, belonging to the field of heat-conducting materials and devices.
Background
In recent years, continuous upgrading of the core processor greatly promotes rapid development in the fields of artificial intelligence, flexible wearing, foldable communication equipment and the like, and the application development of the heat-conducting film material is directly promoted. The core processor is continuously upgraded, the operation speed is continuously accelerated, the calorific value is increased, and the high temperature can generate adverse effects on the service life and the operation speed of the core processor, so that the heat dissipation of the core processor is important, and the heat dissipation material used by the core processor is required to have the characteristic of high heat conduction; meanwhile, equipment such as flexible wearing and the like puts forward urgent needs for high-strength and high-toughness heat dissipation materials. The graphene heat-conducting film has high strength, high flexibility and high heat conductivity, and provides a good foundation for application fields such as artificial intelligence, flexible wearing and foldable communication equipment.
Graphene heat-conducting film materials can be basically divided into three main categories, the first category is obtained by directly preparing graphene powder, carrying out blade coating or spraying after dispersion, drying or film pressing and molding after drying, and the graphene heat-conducting film obtained by the method is low in heat conductivity coefficient due to poor continuity between graphene sheet layers; the second type is the preparation on a substrate by a chemical vapor deposition method, and the graphene heat-conducting film obtained by the method has excellent heat-conducting property, but has the following significant defects: high scale manufacturing cost, difficult transfer and the like; and the third type is that graphene oxide is used as a precursor, and the graphene heat-conducting film is prepared through thermal reduction, chemical reduction, electrochemical reduction and the like.
The graphene oxide film is used as a precursor for preparing the graphene heat-conducting film, the production process is simple and convenient, and the cost is low. Due to the fact that the surface of the graphene oxide has rich oxygen-containing groups, the graphene oxide can be self-assembled to form a macroscopic graphene oxide heat-conducting film, the macroscopic graphene oxide heat-conducting film is used as a precursor, and the graphene oxide heat-conducting film with good sheet continuity can be conveniently prepared through in-situ reduction modes such as thermal reduction, chemical reduction and electrochemical reduction, and the remarkable heat conductivity is given by the continuity of the sheet. Compared with a graphene heat conduction film prepared by a graphene powder compression mold, the graphene heat conduction film prepared by the method has a higher heat conduction coefficient. The method is a preferable scheme for preparing the graphene heat-conducting film in a large scale.
In the process of preparing the graphene heat-conducting film by adopting the third method (taking the graphene oxide film as the precursor), the heat conductivity coefficient of the obtained graphene heat-conducting film is greatly reduced if the reduction is not thorough in the key process of the reduction of the graphene oxide. The graphene heat-conducting film with high heat conductivity is prepared by adopting a thermal reduction mode in general industry, the graphene oxide film is heated to high temperature, the constant temperature is maintained for a period of time under the high-temperature condition, and sp is carried out under the high-temperature condition 3 Carbon will be converted into sp 2 The longer the carbon is maintained, the more the carbon atoms are in ordered arrangement, namely the more the repair of the lamellar defects is facilitated, and the more excellent the heat conductivity of the prepared graphene film is.
In the process of reducing the graphene oxide film to obtain the graphene film, the thermal reduction process is harsh in condition, high-temperature treatment conditions need to be maintained for a long time, and the energy consumption is high; the chemical reduction method is limited by the reducing capability of the reducing agent, and generally only a partially reduced graphene heat-conducting film can be obtained, and the heat conductivity coefficient is relatively low. In chemical reduction, the chemical reducing agent is generally hydrazine hydrate, sodium borohydride, ascorbic acid, citric acid, hydrohalic acid, amino acid, etc., and in order to keep the graphene oxide membrane to be reduced more thoroughly without destroying the dense stacking state and integrity of the original membrane, reduction with hydrohalic acid (HI, HBr, etc.) is often used. The halogen acid reduction mechanism is that halogen replaces oxygen-containing functional groups on graphene oxide sheet layers and then spontaneously eliminates and breaks away from the graphene oxide sheets, but the generated halogen molecules have larger diameters, so that the halogen molecules are difficult to escape from the layers of the graphene film, and the residual halogen molecules are difficult to remove. Generally, the graphene film obtained by the reduction method can cause the inner surface of a container filled with the graphene film to turn yellow and the like in the long-term standing process, because halogen molecules slowly escape and are adsorbed on the surface of the container, and if the halogen molecules escape into the air, serious pollution is caused, which is also a main factor for limiting the large-scale use of the reduction method.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
Aiming at one or more problems in the prior art, the technical problem to be solved by the invention is that in the technology for preparing the graphene heat conducting film by combining chemical reduction and thermal reduction of hydrogen halide, halogen molecules remained between graphene oxide layers are difficult to remove.
The invention provides an impurity removing method for a hydrogen halide reduction graphene oxide film, which comprises the steps of acting hot water on the hydrogen halide reduction graphene oxide film in a fumigating or multiple soaking mode, enabling water molecules to enter the layers of graphene oxide, extruding halogen elements out of the layers of the graphene oxide film, fumigating or multiple soaking for less than 10 hours, and enabling the content of the halogen elements in the graphene oxide film to be less than 0.1%.
After the water is heated, water molecules become active, the movement speed becomes high, and the change direction is frequent. In the process of removing the halogen element, water molecules can frequently enter the interlayer of the graphene oxide by fumigating or soaking for multiple times by using hot water, and the halogen element is extruded out of the interlayer of the graphene oxide film, so that a large amount of halogen element can be rapidly removed in a short time. At the moment, reaction products of the graphene oxide and the hydrogen halide are separated out from the layers of the graphene oxide in a liquid phase form, the generated capillary force enables small molecules to slowly come out from the layers, the thickness of the film is obviously reduced, the structure is more compact, the binding force between the graphene layers is improved, and therefore the flexibility of the reduced graphene film is more excellent.
The conventional soaking and washing mode needs more than 48 hours after water is changed for washing for many times until the washing liquid is colorless, and the content of halogen elements in the graphene oxide film is 0.5-3%. The impurity removal method for removing halogen molecules in the hydrogen halide reduction graphene oxide by adopting the steam fumigation or a small amount of hot water soaking for multiple times only needs less than 10 hours, and the content of halogen elements in the graphene oxide film is less than 0.1%.
According to one aspect of the invention, the graphene oxide film reduced by the hydrogen halide is rinsed before soaking or fumigating;
and/or drying the graphene oxide film reduced by the hydrogen halide after fumigating or soaking for multiple times.
Preferably, the rinsing is performed by using deionized water.
Preferably, the temperature of the drying is 80-120 ℃, preferably 100 ℃.
Further preferably, the drying time is 20-40min, preferably 30min.
According to one aspect of the invention, a multiple soaking method is adopted, and the temperature of the soaked hot water is 40-100 ℃;
and/or soaking for many times until the content of halogen elements is less than 0.1 percent;
and/or the time for soaking in hot water for each time is 20min-2h.
By adopting the method of soaking in hot water for many times, the color change of the solution can be easily observed, the content of halogen elements between graphene oxide membrane layers can be visually monitored, the halogen elements in the solution can be removed in the process of changing water, the content of the halogen elements in the solution is reduced, and the halogen elements between graphene oxide layers can escape more easily.
Preferably, the temperature of the steeped hot water is 80 ℃.
Preferably, the method for soaking for multiple times until the content of halogen elements is less than 0.1% comprises the following steps: after soaking for two hours, the solution is colorless.
Further preferably, the time of each soaking in hot water is 30min.
According to one aspect of the invention, the fumigation is carried out with water vapour.
Preferably, the temperature of the water vapour is in the range 40-150 ℃, preferably 100 ℃.
Preferably, the fumigation is performed under sealed conditions.
Further preferably, the time of fumigation is 4-10h, preferably 6h.
Halogen molecules remained between graphene oxide film layers after hydrogen halide reduction are the biggest limiting factors, and the existence of the halogen molecules can cause the risk of expansion of the film due to bursting during high-temperature thermal reduction treatment in the later period. If the hydrogen halide-reduced graphene oxide film is rinsed by a conventional soaking washing method, it is very difficult to eliminate interlayer halogen. According to the invention, the halogen elements are removed after chemical reduction, so that the halogen elements among graphene oxide layers are removed, the binding force among graphene sheets is higher during heat treatment, and the reduced graphene film has more excellent flexibility.
Due to the step of chemical reduction of the halogen acid, the halogen acid enables the graphene oxide sheets to be stacked more compactly when in-situ reduction occurs, the defects on the graphene sheets are repaired through high-temperature thermal reduction treatment, and the two reduction modes with mutual synergistic effect promote to obtain the graphene heat-conducting film with more excellent heat-conducting property. Meanwhile, the graphene oxide film subjected to in-situ chemical reduction by halogen acid can obtain a graphene heat-conducting film with heat conductivity superior to that of the graphene heat-conducting film subjected to conventional thermal reduction only by less than 50% of energy consumption of conventional thermal treatment. The high-temperature heat treatment time is shortened from 2-4h to 1-2h, the energy is saved, the cost is reduced, and the graphene heat-conducting film with the heat conductivity coefficient of 800-2000W/m.k is obtained.
According to one aspect of the present invention, the method for obtaining the hydrogen halide reduced graphene oxide film by reducing graphene oxide with halogen acid comprises: the graphene oxide film is immersed in a hydrogen halide solution.
Preferably, the hydrogen halide is hydrogen iodide or hydrogen bromide.
Preferably, the concentration of the hydrogen halide solution is between 0.1% and 45%, preferably between 1% and 10%, further preferably 2%.
The weight of the halogen hydride reduced graphene oxide film obtained after every 100 g of the graphene oxide film is reduced by halogen acid is 65-75 g, and 70 g is preferred.
Further preferably, the soaking time in the hydrogen halide solution is 30min-24h, preferably 16h.
The beneficial effects of the invention are:
after the halogen acid in-situ reduction method is adopted, a new washing technology is developed, most of halogen between graphene oxide film layers can be removed by using hot water for removing impurities in a fumigating or multiple soaking mode, the impurity removing efficiency is higher, the content of halogen elements is lower, the halogen residual quantity in the graphene oxide film is less than 0.1%, pollution is less, the binding force between graphene sheet layers is improved, and the flexibility of the reduced graphene film is more excellent. The advantages of the invention are specifically explained from the following aspects:
(1) The chemical reduction and the high-temperature thermal reduction are combined together, the high-temperature thermal treatment time is shortened from 2-4h to 1-2h, and the graphene heat-conducting film with the heat conductivity coefficient of 800-2000W/m.K is obtained; during chemical reduction, the halogen acid adopts an in-situ reduction mode, reaction products obtained by substituting oxygen-containing functional groups on the graphene oxide with halogen during reduction are separated out from the inside of the film in a liquid phase form, the thickness of the film is obviously reduced by the generated capillary force, the structure is more compact, the binding force between graphene sheet layers is improved, and thus the flexibility of the reduced graphene film is more excellent.
(2) After the halogen element replaces the oxygen-containing functional group on the graphene oxide sheet layer, the movement rate of the molecules is improved in a solvent heating mode, and the halogen element is extruded out of the graphene oxide layers through the movement of water molecules, so that the halogen element is eliminated more easily, and more efficiently and quickly. And conventionally soaking the graphene oxide film in normal-temperature water for multiple times, wherein the time for changing water to wash the graphene oxide film until a washing solution is colorless is more than 48 hours, and the content of halogen elements in the graphene oxide film is 0.5-3%. The impurity removal method for removing halogen molecules in the hydrogen halide reduced graphene oxide by means of steam fumigation or a small amount of hot water soaking for multiple times only needs less than 10 hours, and the content of halogen elements in the graphene oxide film is less than 0.1%.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
It should be understood that the preferred embodiments described herein are only for illustrating and explaining the present invention and are not to be considered as limiting the present invention.
As a first embodiment of the present invention, there is provided a method for removing impurities from a hydrogen halide-reduced graphene oxide film, comprising applying hot water to the hydrogen halide-reduced graphene oxide film by fumigation or multiple soaking. The method comprises the following specific steps: leaching the graphene oxide film reduced by the hydrogen halide before soaking or fumigating; and/or drying the graphene oxide film reduced by the hydrogen halide after fumigation or multiple soaking. And the leaching adopts deionized water for leaching. The drying temperature is 80-120 ℃, for example: 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, etc. In a preferred embodiment, the temperature of the drying is 100 ℃. The drying time is 20-40min, for example: 20min, 21min, 22min, 25min, 28min, 30min, 32min, 35min, 38min, 39min, 40min, and the like. In a preferred embodiment, the drying time is 30min.
The method of multiple soaking is adopted, and the temperature of hot water for soaking is 40-100 ℃, for example: 40 ℃, 41 ℃, 42 ℃, 45 ℃, 48 ℃, 49 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, etc.; as a preferred embodiment, the temperature of the soaked hot water is 80 ℃;
and/or, soaking for multiple times until the content of halogen element is less than 0.1%, such as: 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, etc.; soaking for two hours until the solution is colorless;
and/or, the time of each soaking in hot water is 20min-2h, such as: 20min, 21min, 22min, 25min, 28min, 30min, 35min, 40min, 45min, 50min, 55min, 1h10min, 1h20min, 1h30min, 1h40min, 1h50min, 1h55min, 1h56min, 1h57min, 1h58min, 1h59min, 2h, etc.; in a preferred embodiment, the time for each immersion in hot water is 30min.
By adopting the method of soaking in hot water for many times, the color of the solution can be easily observed, the content of halogen elements between graphene oxide film layers can be visually monitored, the halogen elements in the solution can be removed in the process of changing water, the content of the halogen elements in the solution is reduced, and the halogen elements between graphene oxide layers can escape more easily.
The fumigation adopts water vapor for fumigation. The temperature of the water vapor is 40-150 ℃, for example: 40 ℃, 41 ℃, 42 ℃, 45 ℃, 48 ℃, 49 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 146 ℃, 147 ℃, 148 ℃, 149 ℃, 150 ℃, and the like. In a preferred embodiment, the temperature of the water vapor is 100 ℃. The fumigation is carried out under sealed conditions. The time of fumigation is 4-10h, for example: 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, etc. As a preferred embodiment, the time of fumigation is 6h.
After the water is heated, water molecules become active, the movement speed becomes high, and the change direction is frequent. In the process of removing halogen elements, water molecules can frequently enter the interlayer of the graphene oxide in a fumigating or multi-soaking mode by using hot water, the halogen elements are extruded out of the interlayer of the graphene oxide film, and a large amount of halogen elements can be rapidly removed in a short time. At the moment, reaction products of the graphene oxide and the hydrogen halide are separated out from the layers of the graphene oxide in a liquid phase form, the generated capillary force enables the thickness of the film to be obviously reduced, the structure to be more compact, and the binding force between graphene sheet layers is improved, so that the flexibility of the reduced graphene film is more excellent.
The conventional soaking and washing mode needs more than 48 hours after water is changed for washing for many times until the washing liquid is colorless, and the content of halogen elements in the graphene oxide film is 0.5-3%. The impurity removal method for removing halogen molecules in the hydrogen halide reduction graphene oxide by adopting the steam fumigation or a small amount of hot water soaking for multiple times only needs less than 10 hours, and the content of halogen elements in the graphene oxide film is less than 0.1%.
In a second embodiment of the present invention, a reduced graphene oxide film is shown, which is obtained by removing impurities by the impurity removal method of the hydrogen halide reduced graphene oxide film according to the first embodiment of the present invention. The content of halogen element in the reduced graphene oxide film is less than 0.1%, for example: 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, etc.
As a third embodiment of the present invention, a method for preparing a graphene thermal conductive film is presented, including:
reducing graphene oxide by using halogen acid to obtain a hydrogen halide reduced graphene oxide film;
removing impurities from the hydrogen halide reduced graphene oxide film by adopting an impurity removal method of the hydrogen halide reduced graphene oxide film; and
and carrying out high-temperature treatment on the graphene oxide film after impurity removal to obtain the graphene heat-conducting film.
The method for obtaining the hydrogen halide reduced graphene oxide film by reducing the graphene oxide with halogen acid comprises the following steps: the graphene oxide film is immersed in a hydrogen halide solution. The hydrogen halide is hydrogen iodide or hydrogen bromide. The concentration of the hydrogen halide solution is 0.1% to 45%, for example: 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 24%, 25%, 28%, 30%, 35%, 40%, 42%, 43%, 43.5%, 44%, 44.5%, 44.6%, 44.7%, 44.8%, 44.9%, 45%, etc. As a preferred embodiment, the concentration of the hydrogen halide solution is 1% to 10%, for example: 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, 5.2%, 5.5%, 5.8%, 6%, 6.2%, 6.5%, 6.8%, 7%, 7.2%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8%, 9%, 9.2%, 9.5%, 9.8%, 9.9%, 10%, etc. In a most preferred embodiment, the concentration of the hydrogen halide solution is 2%. The weight of the hydrogen halide reduced graphene oxide film obtained after reducing each 100 g of graphene oxide film by halogen acid is 65-75 g, for example: 65 grams, 66 grams, 67 grams, 68 grams, 69 grams, 70 grams, 71 grams, 72 grams, 73 grams, 74 grams, 75 grams, and the like. In a preferred embodiment, the weight of the hydrogen halide reduced graphene oxide film obtained by reducing the graphene oxide film with a halogen acid is 70 g per 100 g of the graphene oxide film. The time for soaking in the hydrogen halide solution is 30min-24h, for example: 30min, 35min, 40min, 45min, 50min, 55min, 1h, 2h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 21h, 22h, 23h, 24h and the like. In a preferred embodiment, the immersion time in the hydrogen halide solution is 16 hours. The temperature of the high-temperature treatment is 2000-3000 ℃, for example: 2000 deg.C, 2010 deg.C, 2020 deg.C, 2030 deg.C, 2040 deg.C, 2050 deg.C, 2100 deg.C, 2200 deg.C, 2300 deg.C, 2400 deg.C, 2500 deg.C, 2600 deg.C, 2700 deg.C, 2800 deg.C, 2850 deg.C, 2900 deg.C, 2950 deg.C, 2960 deg.C, 2970 deg.C, 2980 deg.C, 2990 deg.C, 3000 deg.C, etc. In a preferred embodiment, the temperature of the high-temperature treatment is 2900 ℃. The time of the high-temperature treatment is 1-2h, for example: 1h, 1h10min, 1h20min, 1h30min, 1h40min, 1h50min, 2h, etc. The temperature rise rate of the high-temperature treatment is 0.5-3 ℃/min, for example: 0.5 deg.C/min, 0.6 deg.C/min, 0.7 deg.C/min, 0.8 deg.C/min, 0.9 deg.C/min, 1 deg.C/min, 1.2 deg.C/min, 1.3 deg.C/min, 1.5 deg.C/min, 1.8 deg.C/min, 2 deg.C/min, 2.1 deg.C/min, 2.2 deg.C/min, 2.4 deg.C/min, 2.5 deg.C/min, 2.7 deg.C/min, 2.8 deg.C/min, 2.9 deg.C/min, 3 deg.C/min, etc. In a preferred embodiment, the temperature increase rate of the high-temperature treatment is 1 ℃/min.
According to the invention, two reduction modes of chemical reduction and high-temperature thermal reduction are combined together, the graphene oxide film is pretreated under mild conditions by using the chemical reduction, and the reduction degree is improved by heat treatment, so that the graphene heat-conducting film with high heat conductivity is finally prepared. Due to the step of chemical reduction of the halogen acid, the halogen acid enables the graphene oxide sheets to be stacked more compactly when in-situ reduction occurs, the defects on the graphene sheets are repaired through high-temperature thermal reduction treatment, and the two reduction modes with synergistic effect mutually promote to obtain the graphene heat-conducting film with more excellent heat-conducting property. Meanwhile, the graphene oxide film subjected to the in-situ chemical reduction of the halogen acid can obtain the graphene heat-conducting film with the heat conductivity superior to that of the graphene heat-conducting film subjected to the conventional thermal reduction only by less than 50% of the energy consumption of the conventional thermal treatment. The high-temperature heat treatment time is shortened from 2-4h to 1-2h, the energy is saved, the cost is reduced, and the graphene heat-conducting film with the heat conductivity coefficient of 800-2000W/m.k is obtained.
Halogen molecules remained between graphene oxide film layers after hydrogen halide reduction are the biggest limiting factors, and the existence of the halogen molecules can cause the risk of expansion of the film due to bursting during high-temperature thermal reduction treatment in the later period. If the hydrogen halide-reduced graphene oxide film is rinsed by a conventional soaking washing method, it is very difficult to eliminate interlayer halogen. According to the invention, the halogen elements are removed after chemical reduction, so that the halogen elements among graphene oxide layers are removed, the binding force among graphene sheets is higher during heat treatment, and the reduced graphene film has more excellent flexibility.
As a fourth embodiment of the present invention, a graphene thermal conductive film is shown, wherein the graphene thermal conductive film is prepared by the method for preparing a graphene thermal conductive film according to the third embodiment of the present invention. The thermal conductivity coefficient of the graphene thermal conductive film is 800-2000W/m.k, for example: 800W/m.k, 810W/m.k, 820W/m.k, 830W/m.k, 840W/m.k, 850W/m.k, 860W/m.k, 870W/m.k, 880W/m.k, 890W/m.k, 900W/m.k, 1000W/m.k, 1100W/m.k, 1200W/m.k, 1300W/m.k, 1400W/m.k, 1500W/m.k, 1600W/m.k, 1700W/m.k, 1800W/m.k, 1900W/m.k, 1950W/m.k, 1960W/m.k, 1970W/m.k, 1980W/m.k, 1990W/m.k, 2000W/m.k, and the like.
The advantages of the invention are illustrated below by way of examples and comparative examples:
example 1A:
the embodiment shows an impurity removal method for reducing a graphene oxide film by using halogen acid.
Step 1):
10 graphene oxide films with the same size of 10cm by 10cm are taken and soaked in HI solution with the content of 0.1% for 24h to obtain the hydrogen halide reduced graphene oxide film with metallic luster.
Step 2):
soaking the graphene oxide film reduced by the hydrogen halide prepared in the step 1) in hot water at 80 ℃ for 30min, then replacing the hot water at 80 ℃, and circulating the steps until the hot water soaked by the graphene oxide film reduced by the hydrogen halide is colorless within 2 hours.
Step 3):
and (3) drying the hydrogen halide reduced graphene oxide film subjected to impurity removal in the step 2) in an oven at 100 ℃ for 30min.
And (3) performing scanning test by using a scanning electron microscope with an energy spectrometer, and performing qualitative and quantitative analysis on element distribution of a microscopic region of the material to obtain that the average iodine content of the 10 hydrogen halide reduced graphene oxide films is 0.03%.
Example 1B:
this example illustrates a method of preparing a graphene thermal conductive film using the graphene oxide film prepared by the impurity removal method of example 1A.
And (2) carrying out high-temperature thermal reduction on the graphene oxide film prepared in the embodiment 1A at the temperature of 2000-3000 ℃ for 1-2h to obtain the graphene heat-conducting film.
Through tests, the average thermal conductivity of 10 graphene thermal conductive films is 1217W/m.k.
Example 2A:
the embodiment shows an impurity removal method for reducing a graphene oxide film by using halogen acid.
Step 1):
10 pieces of graphene oxide films with the same size of 10cm by 10cm are taken and soaked in a HI solution with the content of 45% for 30min to obtain the hydrogen halide reduced graphene oxide film with metallic luster.
Step 2):
soaking the hydrogen halide reduced graphene oxide film prepared in the step 1) in hot water at 40 ℃ for 40min, then replacing the hot water at 40 ℃, and circulating the steps until the hot water soaked by the hydrogen halide reduced graphene oxide film is colorless within 2 hours.
Step 3):
drying the hydrogen halide reduced graphene oxide film subjected to impurity removal in the step 2) in an oven at 100 ℃ for 30min.
And (3) performing scanning test by using a scanning electron microscope with an energy spectrometer, and performing qualitative and quantitative analysis on element distribution of a microscopic region of the material to obtain the average iodine content of 0.07 percent of 10 hydrogen halide reduced graphene oxide films.
Example 2B:
this example illustrates a method for preparing a graphene thermal conductive film using the graphene oxide film prepared by the impurity removal method of example 2A.
And (3) carrying out high-temperature thermal reduction on the graphene oxide film prepared in the embodiment 2A at 2000-3000 ℃ for 1-2h to obtain the graphene heat-conducting film.
Through tests, the average thermal conductivity of 10 graphene thermal conductive films is 1327W/m.k.
Example 3A:
the embodiment shows an impurity removal method for reducing a graphene oxide film by using halogen acid.
Step 1):
10 pieces of graphene oxide films with the same size of 10cm by 10cm are soaked in an HBr solution with the content of 0.2% for 24h to obtain the hydrogen halide reduced graphene oxide film with metallic luster.
Step 2):
soaking the hydrogen halide reduced graphene oxide film prepared in the step 1) in hot water at 90 ℃ for 20min, then replacing the hot water at 90 ℃, and circulating the steps until the hot water soaked by the hydrogen halide reduced graphene oxide film is colorless within 2 hours.
Step 3):
and (3) drying the hydrogen halide reduced graphene oxide film subjected to impurity removal in the step 2) in an oven at 100 ℃ for 30min.
And (3) performing scanning test by using a scanning electron microscope with an energy spectrometer, and performing qualitative and quantitative analysis on element distribution of a microscopic region of the material to obtain the average bromine content of the 10 hydrogen halide reduced graphene oxide films, which is 0.02%.
Example 3B:
this example illustrates a method of preparing a graphene thermal conductive film using the graphene oxide film prepared by the impurity removal method of example 3A.
And (3) carrying out high-temperature thermal reduction on the graphene oxide film prepared in the embodiment 3A at the temperature of 2000-3000 ℃ for 1-2h to obtain the graphene heat-conducting film.
Through tests, the average thermal conductivity of 10 graphene thermal conductive films is 1283W/m.k.
Example 4A:
the embodiment shows an impurity removal method for reducing a graphene oxide film by using halogen acid.
Step 1):
10 pieces of graphene oxide films with the same size of 10cm by 10cm are soaked in an HBr solution with the content of 45% for 30min to obtain the hydrogen halide reduced graphene oxide film with metallic luster.
Step 2):
soaking the hydrogen halide reduced graphene oxide film prepared in the step 1) in hot water at 80 ℃ for 20min, then replacing the hot water at 80 ℃, and circulating the steps until the hot water soaked by the hydrogen halide reduced graphene oxide film is colorless within 2 hours.
Step 3):
drying the hydrogen halide reduced graphene oxide film subjected to impurity removal in the step 2) in an oven at 100 ℃ for 30min.
And (3) performing scanning test by using a scanning electron microscope with an energy spectrometer, and performing qualitative and quantitative analysis on element distribution of a microscopic region of the material to obtain the average bromine content of the 10 hydrogen halide reduced graphene oxide films, which is 0.05%.
Example 4B:
this example illustrates a method for preparing a graphene thermal conductive film using the graphene oxide film prepared by the impurity removal method of example 4A.
And (3) carrying out high-temperature thermal reduction on the graphene oxide film prepared in the embodiment 4A at 2000-3000 ℃ for 1-2h to obtain the graphene heat-conducting film.
Through testing, the average thermal conductivity of 10 graphene thermal conductive films is 1345W/m.k.
Example 5A:
the embodiment shows an impurity removal method for reducing a graphene oxide film by using halogen acid.
Step 1):
10 pieces of graphene oxide films with the same size of 10cm by 10cm are taken and soaked in HI solution with the content of 2% for 16h, and the hydrogen halide reduced graphene oxide film with metallic luster is obtained.
Step 2):
putting the graphene oxide film reduced by the hydrogen halide prepared in the step 1) under the condition of hot water vapor for continuous fumigation for 6 hours.
Step 3):
drying the hydrogen halide reduced graphene oxide film subjected to impurity removal in the step 2) in an oven at 100 ℃ for 30min.
And (3) performing scanning test by using a scanning electron microscope with an energy spectrometer, and performing qualitative and quantitative analysis on element distribution of a microscopic region of the material to obtain the average iodine content of 0.08 percent of 10 hydrogen halide reduced graphene oxide films.
Example 5B:
this example illustrates a method of preparing a graphene thermal conductive film using the graphene oxide film prepared by the impurity removal method of example 5A.
And (3) carrying out high-temperature thermal reduction on the graphene oxide film prepared in the embodiment 5A at 2000-3000 ℃ for 1-2h to obtain the graphene heat-conducting film.
Through tests, the average thermal conductivity of 10 graphene thermal conductive films is 1227W/m.k.
Comparative example 6:
the present comparative example shows a method for preparing a graphene thermal conductive film using a thermal reduction method.
And (3) performing high-temperature thermal reduction on 10 graphene oxide films with the same size of 10cm to 10cm at the temperature of 2000-3000 ℃ for 1-2h to obtain the graphene heat conduction film.
Through testing, the average thermal conductivity coefficient of 10 graphene heat-conducting films is 985W/m.k.
Comparative example 7:
the present comparative example shows a method for preparing a graphene thermal conductive film using a thermal reduction method.
And (3) performing high-temperature thermal reduction on 10 graphene oxide films with the same size of 10cm by 10cm at the temperature of 2000-3000 ℃ for 2-4h to obtain the graphene heat-conducting film.
Through testing, the average thermal conductivity of 10 graphene thermal conductive films is 1156W/m.k.
Comparative example 8A:
this example shows a conventional method for removing impurities by reducing graphene oxide film with halogen acid.
Step 1):
10 pieces of graphene oxide films with the same size of 10cm by 10cm are taken and soaked in HI solution with the content of 2% for 16h, and the hydrogen halide reduced graphene oxide film with metallic luster is obtained.
Step 2):
soaking and leaching the hydrogen halide reduced graphene oxide film prepared in the step 1) with deionized water for more than 10 times at 20 ℃, wherein the soaking time is 1h each time.
Step 3):
drying the hydrogen halide reduced graphene oxide film subjected to impurity removal in the step 2) in an oven at 100 ℃ for 30min.
And (3) performing scanning test by using a scanning electron microscope with an energy spectrometer, and performing qualitative and quantitative analysis on element distribution of a microscopic region of the material to obtain the average iodine content of 0.96% in 10 hydrogen halide reduced graphene oxide films.
Comparative example 8B:
this example illustrates a method of preparing a graphene thermal conductive film using the graphene oxide film prepared by the impurity removal method of example 8A.
The graphene oxide film prepared in example 8A was subjected to high temperature thermal reduction at 2000-3000 ℃ for 1-2 hours.
The average thermal conductivity of 10 graphene thermal conductive films is 1128W/m.k.
From the examples 1 to 5, it can be seen that by using the method of chemical reduction-impurity removal-thermal reduction of hydrogen halide provided by the invention, the content of halogen element after impurity removal is 0.03% -0.08%, and the graphene heat-conducting film with the average heat conductivity coefficient in the range of 1217-1345W/m.k can be obtained only by performing high-temperature treatment for 1-2h. In comparative example 6, the average thermal conductivity of the graphene thermal conductive film is 985W/m.k under the condition of high-temperature treatment for 1-2h by only adopting a one-step thermal reduction method. In comparative example 7, the average thermal conductivity of the graphene thermal conductive film is 1156W/m.k under the condition of high-temperature treatment for 2-4h by only adopting a one-step thermal reduction method. Therefore, the reduction efficiency is not high by adopting a one-step thermal reduction method, and the thermal conductivity of the prepared graphene thermal conductive film is not good. The comparative example 8 adopts a method of chemical reduction of hydrogen halide, conventional impurity removal and thermal reduction, the impurity removal process is long, the impurity removal effect is poor, the content of halogen element is 0.96%, the heat conductivity coefficient of the prepared graphene heat-conducting film is 1128W/m.k, and the heat conductivity is inferior to that of the graphene heat-conducting film provided by the invention.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. An impurity removal method for reducing a graphene oxide film by using hydrogen halide is characterized by comprising the following steps: the method comprises the steps of acting on a hydrogen halide reduced graphene oxide film by hot water in a fumigating or multi-soaking mode, enabling water molecules to enter the interlayer of graphene oxide, extruding halogen elements out of the interlayer of the graphene oxide film, fumigating or multi-soaking for less than 10 hours, and enabling the content of the halogen elements in the graphene oxide film to be less than 0.1%.
2. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 1, comprising: leaching the graphene oxide film reduced by the hydrogen halide before soaking or fumigating; and/or drying the graphene oxide film reduced by the hydrogen halide after fumigating or soaking for multiple times.
3. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 2, wherein: and the leaching adopts deionized water for leaching.
4. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 2, wherein: the drying temperature is 80-120 ℃.
5. The method for removing impurities from a graphene oxide film reduced with hydrogen halide according to claim 4, wherein: the drying temperature is 100 ℃.
6. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 2, wherein: the drying time is 20-40min.
7. The method for removing impurities from a graphene oxide film reduced with hydrogen halide according to claim 6, wherein: the drying time is 30min.
8. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 1, comprising: adopting a method of multiple soaking, wherein the temperature of the soaked hot water is 40-100 ℃;
and/or, soaking for multiple times until the content of halogen elements is less than 0.1%;
and/or the time for soaking in hot water for each time is 20min-2h.
9. The method for removing impurities by reducing a graphene oxide film with hydrogen halide according to claim 8, wherein: the temperature of the soaked hot water is 80 ℃.
10. The method for removing impurities from a graphene oxide film reduced with hydrogen halide according to claim 8, wherein: after soaking for two hours, the solution is colorless.
11. The method for removing impurities by reducing a graphene oxide film with hydrogen halide according to claim 8, wherein: the time for soaking in hot water is 30min each time.
12. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 1, comprising: the fumigation adopts water vapor for fumigation.
13. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 12, wherein: the temperature of the water vapor is 40-150 ℃.
14. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 13, wherein: the temperature of the water vapor was 100 ℃.
15. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 12, wherein: the fumigation is carried out under sealed conditions.
16. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 12, wherein: the time of fumigation is 4-10h.
17. The impurity removal method for reducing a graphene oxide film with hydrogen halide according to claim 16, wherein: the time of fumigation is 6h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255670A (en) * | 2012-02-20 | 2013-08-21 | 海洋王照明科技股份有限公司 | Method for preparing graphene paper through utilizing electric field guidance |
| US20140371443A1 (en) * | 2012-02-15 | 2014-12-18 | Arizona Board of Regents, a Body Corporate of the State of Arizona Acting for and on behalf of ASU | Multifunctional Materials And Composites |
| CN105542333A (en) * | 2015-12-15 | 2016-05-04 | 东华大学 | Reduced graphene oxide composite film and preparation method thereof |
| CN106132872A (en) * | 2014-03-28 | 2016-11-16 | 曼彻斯特大学 | The graphene oxide barrier material of reduction |
| CN106986335A (en) * | 2017-04-11 | 2017-07-28 | 杭州高烯科技有限公司 | A kind of flexible graphene oxide membrane and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102254582B (en) * | 2010-05-18 | 2013-05-15 | 国家纳米科学中心 | Graphite alkenyl conductive material and preparation method thereof |
| CN104030275B (en) * | 2014-05-30 | 2016-08-24 | 上海应用技术学院 | A kind of preparation method of redox graphene heat conduction thin film |
| KR102325601B1 (en) * | 2015-03-02 | 2021-11-15 | 솔베이스페셜티폴리머스코리아 주식회사 | A method for preparing a fluorinated composite, a fluorinated composite prepared therefrom, and a barrier layer comprising the same |
| CZ2016815A3 (en) * | 2016-12-21 | 2018-04-04 | Vysoké Učení Technické V Brně | A method of preparing graphene hydrogel |
| CN107337199A (en) * | 2017-07-17 | 2017-11-10 | 山西大学 | A kind of preparation method of the graphene film electrode material of ultracapacitor |
| CN108516538B (en) * | 2018-04-20 | 2020-01-10 | 北京航空航天大学 | Preparation method of pi-bond and covalent-bond orderly-crosslinked superstrong high-conductivity graphene composite film |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140371443A1 (en) * | 2012-02-15 | 2014-12-18 | Arizona Board of Regents, a Body Corporate of the State of Arizona Acting for and on behalf of ASU | Multifunctional Materials And Composites |
| CN103255670A (en) * | 2012-02-20 | 2013-08-21 | 海洋王照明科技股份有限公司 | Method for preparing graphene paper through utilizing electric field guidance |
| CN106132872A (en) * | 2014-03-28 | 2016-11-16 | 曼彻斯特大学 | The graphene oxide barrier material of reduction |
| CN105542333A (en) * | 2015-12-15 | 2016-05-04 | 东华大学 | Reduced graphene oxide composite film and preparation method thereof |
| CN106986335A (en) * | 2017-04-11 | 2017-07-28 | 杭州高烯科技有限公司 | A kind of flexible graphene oxide membrane and preparation method thereof |
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