CN111747401A - Preparation method of fluorinated graphene material - Google Patents
Preparation method of fluorinated graphene material Download PDFInfo
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- CN111747401A CN111747401A CN201910243489.8A CN201910243489A CN111747401A CN 111747401 A CN111747401 A CN 111747401A CN 201910243489 A CN201910243489 A CN 201910243489A CN 111747401 A CN111747401 A CN 111747401A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 64
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 26
- 239000011737 fluorine Substances 0.000 claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 230000021523 carboxylation Effects 0.000 abstract description 5
- 238000006473 carboxylation reaction Methods 0.000 abstract description 5
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract description 2
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract description 2
- 238000000502 dialysis Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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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
- C01B32/184—Preparation
-
- 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
- C01B32/10—Carbon fluorides, e.g. [CF]nor [C2F]n
Abstract
The invention discloses a preparation method of a fluorinated graphene material, which comprises the steps of firstly carrying out functionalization treatment on graphene by utilizing a carboxylation method to obtain carboxylated graphene, and then carrying out fluorine element substitution on hydroxyl on carboxyl on the surface of the graphene by utilizing a decarboxylation substitution method to obtain the fluorinated graphene. Through characterization and analysis, the fluorine element is successfully grafted on the surface of the graphene, the molar grafting rate can reach 15%, and the fluorinated graphene has a complete surface and is not obviously structurally damaged. The invention provides a method and application premise for fluorinated graphene.
Description
Technical Field
The invention belongs to the field of carbon nano composite materials, and particularly relates to a preparation method of a fluorinated graphene material.
Background
Graphene is the most attractive new two-dimensional material discovered recently, and has acquired the 2010 nobel prize, and its excellent physical and chemical properties have led researchers to pay great attention to it today. Meanwhile, research products of various graphene are also greatly applied to scientific social life. The composite material taking GO as a substrate is a research angle for development and utilization of graphene, and particularly has a very wide application prospect in the fields of liquid crystal devices, photoelectric information storage, electronic devices, sensing materials, catalysts and the like.
The problem of dispersibility of graphene has been one of the topics of scientific interest, because graphene as an excellent carrier itself provides limited performance, and a functional group must be grafted to bring the scientific application of the new material into full play. Moreover, the quality of life of people is continuously improved, and the issues of energy storage, environmental friendliness and the like become more and more sensitive, so that the development of energy storage environment-friendly materials becomes very important. Through long-time research, the method for covalent bond functionalization is found to be capable of grafting the group with the fluorine element on the surface of the graphene, and shows higher energy storage density, better surface contact effect and the like. And the fluorinated graphene molecules can be subjected to composite treatment with various materials to obtain different types of graphene composite materials, such as fluorinated graphene/self-repairing polymer materials, fluorinated graphene/polypyrrole composite materials and the like. Therefore, the preparation method or the process for obtaining the fluorinated graphene has great potential in the aspects of energy storage, material corrosion prevention, aerospace equipment and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a preparation method of a fluorinated graphene material, and is used for polymer framework materials, battery anode and cathode materials, quantum dots and the like in the future, so that the preparation method has a wide application prospect.
The technical purpose of the invention is realized by the following technical scheme.
Firstly, reacting graphene oxide, sodium hydroxide and sodium chloroacetate to convert hydrogen atoms of hydroxyl groups in the graphene oxide into carboxyl groups, so as to obtain carboxylated graphene; and then reacting the carboxylated graphene, a fluorine source substance and silver nitrate to replace hydroxyl in carboxyl in the carboxylated graphene by fluorine atoms to obtain the fluorinated graphene.
In addition, the sodium hydroxide provides an alkaline environment for the reaction, enhances the hydrolysis, and reacts with the residual chloroacetic acid in the sodium chloroacetate to form corresponding salt, thereby avoiding the influence of the addition of other ions.
Further, sodium hydroxide and sodium chloroacetate were in equimolar ratio.
In addition, when graphene oxide, sodium hydroxide and sodium chloroacetate are reacted, water is selected as a reaction atmosphere, stirring reaction is carried out at room temperature of 20-25 ℃, and the reaction time is 6-15 hours, preferably 8-12 hours; stirring is carried out by selecting ultrasound or machinery.
And after obtaining the carboxylated graphene, centrifuging the product, washing the product twice by absolute ethyl alcohol, centrifuging the product, washing the product by deionized water, dialyzing the product in a dialysis bag, and drying the product at the temperature of 60-70 ℃.
Further, the fluorine source substance is a commercially available fluorine-containing reagent, sodium fluoride reagent or high-purity fluorine gas.
The mass ratio of the carboxylated graphene to the fluorine source substance to the silver nitrate is 1: (3-8): 1, preferably 1: (5-8): 1.
in addition, when the carboxylated graphene, the fluorine source substance and the silver nitrate react, water is selected as a reaction atmosphere, inert protective gas is filled after vacuum pumping, reflux reaction is carried out at 80-90 ℃, and the reaction time is 20-24 hours;
and after the reaction of the carboxylated graphene, the fluorine source substance and the silver nitrate is finished, cooling to room temperature, then carrying out suction filtration on the obtained solution, washing filter residues with deionized water and absolute ethyl alcohol, then putting the washed solution into a dialysis bag for dialysis, and carrying out freeze drying for 24 hours after 3-5 days (24 hours per day) of dialysis to obtain the fluorinated graphene.
In the finally prepared fluorinated graphene material, fluorine is grafted on the surface of graphene in a covalent bond mode, the molar grafting rate is 10-15%, and F-C (carbon atom of carbonyl) -O-graphene is adopted.
Compared with the prior art, the technical scheme of the invention is that firstly, the graphene is functionalized by using a carboxylation method to obtain the carboxylated graphene, and then, hydroxyl on the carboxyl on the surface of the graphene is substituted by fluorine element by using a decarboxylation substitution method to obtain the fluorinated graphene. Through characterization and analysis, the fluorine element is successfully grafted on the surface of the graphene, the molar grafting rate can reach 15%, and the fluorinated graphene has a complete surface and is not obviously structurally damaged. The invention provides a method and application premise for fluorinated graphene.
Drawings
Fig. 1 is an X-ray energy spectrum of fluorinated graphene; ultraviolet spectrograms of graphene oxide, carboxylated graphene and fluorinated graphene.
Fig. 2 is an infrared spectrum of graphene oxide, carboxylated graphene, and fluorinated graphene.
Fig. 3 is a scanning electron micrograph of fluorinated graphene prepared according to the present invention.
FIG. 4 is a schematic view of a specific process of the preparation method of the present invention.
Fig. 5 is a schematic diagram of a chemical formula structure of a fluorinated graphene material prepared according to the present invention.
Detailed Description
The following embodiments are further described in the present invention, but not intended to limit the scope of the invention. Drugs were purchased from alatin, llc.
Example 1
1) Carboxylation of Graphene Oxide (GO): diluting the graphene oxide aqueous suspension, and then carrying out water bath ultrasound. Adding sodium hydroxide and sodium chloroacetate in a molar ratio of 1:1 into the GO dispersion liquid, performing water bath ultrasonic treatment for 2h, stirring at room temperature for 12h, and converting hydrogen atoms of hydroxyl groups in GO into carboxyl groups under the action of conjugated acetic acid groups of GO and sodium chloroacetate to obtain carboxylated graphene. Then centrifuging the product, washing twice with absolute ethyl alcohol, centrifuging, washing with deionized water, dialyzing in a dialysis bag, and drying at 65 ℃.
2) Preparing a fluorinated graphene material: carboxylated graphene, fluorine-containing reagent and AgNO in a mass ratio of 1:5:13Mixing in a three-neck flask for ultrasonic treatment, the reaction AgNO3And (3) vacuumizing and filling Ar to ensure the inert protective gas atmosphere for the catalyst, and repeating the process for three times, wherein each time is 5 min. Then adding deionized water, and carrying out oil bath at 90 DEG CAnd (3) reacting and refluxing for 24h under the environment, and cooling to room temperature of 20 ℃ after the reaction is finished so as to replace hydroxyl in carboxyl in the carboxylated graphene by fluorine atoms. And then carrying out suction filtration on the obtained solution, washing filter residues with deionized water and absolute ethyl alcohol, putting the washed solution into a dialysis bag for dialysis, and carrying out freeze drying for 24 hours after dialysis for 5 days to obtain the fluorinated graphene.
Example 2
1) Carboxylation of Graphene Oxide (GO): diluting the (oxidized) graphene aqueous suspension, and then carrying out water bath ultrasound. Adding sodium hydroxide and sodium chloroacetate in a molar ratio of 1:1 into a proper amount of GO dispersion liquid, performing water bath ultrasonic treatment for 1h, stirring at room temperature for 12h, and converting hydrogen atoms of hydroxyl groups in GO into carboxyl groups under the action of conjugated acetic acid groups of GO and sodium chloroacetate to obtain carboxylated graphene. Then centrifuging the product, washing twice with absolute ethyl alcohol, centrifuging, washing with deionized water, dialyzing in a dialysis bag, and drying at 65 ℃.
2) Preparing a fluorinated graphene material: carboxylated graphene, a sodium fluoride reagent and AgNO in a mass ratio of 1:5:13Mixing in a three-neck flask for ultrasonic dispersion, vacuumizing, and charging Ar, and repeating the process for 3min three times. And then adding deionized water, reacting and refluxing for 24 hours in an oil bath environment at 90 ℃, and cooling to room temperature after the reaction is finished. And then carrying out suction filtration on the obtained solution, washing filter residues with deionized water and absolute ethyl alcohol, putting the washed solution into a dialysis bag for dialysis, and carrying out freeze drying for 24 hours after 3 days of dialysis to obtain the fluorinated graphene.
Example 3
1) Carboxylation of Graphene Oxide (GO): diluting the (oxidized) graphene aqueous suspension, and then carrying out water bath ultrasound. Adding sodium hydroxide and sodium chloroacetate in a molar ratio of 1:1 into a proper amount of GO dispersion liquid, performing water bath ultrasonic treatment for 1.5h, stirring at room temperature for 10h, and converting hydrogen atoms of hydroxyl groups in GO into carboxyl groups under the action of conjugated acetic acid groups of GO and sodium chloroacetate to obtain carboxylated graphene. Then centrifuging the product, washing twice with absolute ethyl alcohol, centrifuging, washing with deionized water, dialyzing in a dialysis bag, and drying at 65 ℃.
2) Preparing a fluorinated graphene material: carboxylated graphene, high-purity fluorine gas and AgNO in a mass ratio of 1:5:13The sonication was performed in a three-necked flask with mixing, and the process was repeated three times for 4min each time. The reaction was carried out in an oil bath at 90 ℃ and refluxed for 24h, and then cooled to room temperature after the reaction was completed. And then carrying out suction filtration on the obtained solution, washing filter residues with deionized water and absolute ethyl alcohol, putting the washed solution into a dialysis bag for dialysis, and carrying out freeze drying for 20 hours after dialysis for 4 days to obtain the fluorinated graphene.
The fluorinated graphene prepared according to the present invention was characterized as follows. The first figure is an ultraviolet-visible absorption spectrum diagram of graphene oxide, carboxylated graphene and fluorinated graphene. The three show two characteristic absorption peaks at 200-300 nm. The absorption peak at 230nm corresponds to the pi → pi transition of the C ═ C bond, and the absorption peak at 290nm corresponds to the n → pi transition of the C ═ O bond. Furthermore, the absorption peak of the fluorinated graphene at 400nm is n → sigma transition of C-F bond, which can prove the existence of fluorine element. And the second graph is an infrared spectrum of the graphene oxide, the carboxylated graphene and the fluorinated graphene. As can be seen from the figure, the graphene oxide is 1600cm-1And an absorption peak appears, and is a stretching vibration peak of C ═ C bond. At 1700cm-1The absorption peak is also evident here, here the stretching vibration peak of the C ═ O bond. At 3400cm-1An absorption peak appears, which is a stretching vibration peak of-OH. At 1100cm-1There appears a distinct absorption peak, here the stretching vibration peak of the C-O-C bond. And the spectra of GO and GO-COOH are compared, the-OH stretching vibration peak (3400 cm)-1Position) and C ═ O bond (1700 cm)-1Where) are very distinct and intense, the absorption peaks of the C-O-C groups are greatly reduced and the patterns of GO-COOH are 2300cm-1The absorption peak appeared here is the O — H bond in the carboxyl group, indicating the presence of the carboxyl group in graphene. I.e.the C-O-C group has been carboxylated. The spectra of GO-COOH and GF were compared, with GF at 976cm-1A strong absorption peak exists, namely a stretching vibration peak of a C-F bond in GF, which proves that fluorine elements exist in the fluorinated graphene. Figure three is a sweep of fluorinated grapheneIn a scanning electron microscope image, it can be seen that the graphene nanoplatelets are transparent and have clear fold shapes under high magnification of the fluorinated graphene, and the fluorinated graphene in the process is proved to be very thin. Meanwhile, the lamella is complete, and no obvious structural damage is found, so that the process is proved to be excellent. The molar grafting ratio is 10 to 15 percent by calculating the weight loss ratio by using a thermogravimetric analyzer.
The preparation of the fluorinated graphene can be realized by adjusting the process parameters according to the content of the invention, and the performance basically consistent with the invention is shown. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The preparation method of the fluorinated graphene material is characterized by comprising the following steps of firstly, reacting graphene oxide, sodium hydroxide and sodium chloroacetate to convert hydrogen atoms of hydroxyl groups in the graphene oxide into carboxyl groups, so as to obtain carboxylated graphene; and then reacting the carboxylated graphene, a fluorine source substance and silver nitrate to replace hydroxyl in carboxyl in the carboxylated graphene by fluorine atoms to obtain the fluorinated graphene.
2. The method for preparing a fluorinated graphene material according to claim 1, wherein the molar ratio of sodium hydroxide to sodium chloroacetate is equal when graphene oxide, sodium hydroxide and sodium chloroacetate react.
3. The method for preparing a fluorinated graphene material according to claim 1, wherein when graphene oxide, sodium hydroxide and sodium chloroacetate are reacted, water is selected as a reaction atmosphere, stirring reaction is performed at room temperature of 20-25 ℃, and ultrasonic or mechanical stirring is selected.
4. The method of claim 1, wherein the reaction time of graphene oxide, sodium hydroxide and sodium chloroacetate is 6-15 hours, preferably 8-12 hours.
5. The method of claim 1, wherein the fluorine source is a commercially available fluorine-containing reagent, sodium fluoride reagent, or high purity fluorine gas.
6. The method according to claim 1, wherein when the carboxylated graphene, the fluorine source substance and the silver nitrate are reacted, the mass ratio of the carboxylated graphene to the fluorine source substance to the silver nitrate is 1: (3-8): 1, preferably 1: (5-8): 1.
7. the method according to claim 1, wherein when the carboxylated graphene, the fluorine source substance and the silver nitrate are reacted, water is selected as a reaction atmosphere, vacuum pumping is performed, an inert protective gas is filled, and a reflux reaction is performed at 80-90 ℃ for 20-24 hours.
8. The fluorinated graphene material obtained by the production method according to any one of claims 1 to 7, wherein fluorine is grafted to the surface of graphene in the form of a covalent bond.
9. The fluorinated graphene material of claim 8, wherein the fluorine atom is bonded to the graphene as "F — C (carbon atom of carbonyl) -O —".
10. The fluorinated graphene material of claim 8 or 9, wherein the molar grafting ratio is 10% to 15%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687873A (en) * | 2020-12-23 | 2021-04-20 | 湖南永盛新材料股份有限公司 | Preparation method of high-specific-energy lithium battery |
| CN114368745A (en) * | 2021-09-17 | 2022-04-19 | 浙江理工大学上虞工业技术研究院有限公司 | Graphene oxide, preparation method and application |
| US20220371897A1 (en) * | 2021-05-24 | 2022-11-24 | Sgraphene | Graphene nanopore manufacturing method using detachable functional groups and graphene sheet having graphene nanoholes formed thereby |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420352A (en) * | 2013-08-08 | 2013-12-04 | 四川大学 | High-fluoride-content graphite fluoride and preparation method thereof |
| CN104964961A (en) * | 2015-06-08 | 2015-10-07 | 上海交通大学 | Preparation method and application of graphene oxide-gold nano-rod composite nano-material |
| CN106421804A (en) * | 2016-10-21 | 2017-02-22 | 曲阜师范大学 | Fluorinated graphene nanometer medicine carrier, and preparation method and application thereof |
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- 2019-03-28 CN CN201910243489.8A patent/CN111747401A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420352A (en) * | 2013-08-08 | 2013-12-04 | 四川大学 | High-fluoride-content graphite fluoride and preparation method thereof |
| CN104964961A (en) * | 2015-06-08 | 2015-10-07 | 上海交通大学 | Preparation method and application of graphene oxide-gold nano-rod composite nano-material |
| CN106421804A (en) * | 2016-10-21 | 2017-02-22 | 曲阜师范大学 | Fluorinated graphene nanometer medicine carrier, and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687873A (en) * | 2020-12-23 | 2021-04-20 | 湖南永盛新材料股份有限公司 | Preparation method of high-specific-energy lithium battery |
| US20220371897A1 (en) * | 2021-05-24 | 2022-11-24 | Sgraphene | Graphene nanopore manufacturing method using detachable functional groups and graphene sheet having graphene nanoholes formed thereby |
| CN114368745A (en) * | 2021-09-17 | 2022-04-19 | 浙江理工大学上虞工业技术研究院有限公司 | Graphene oxide, preparation method and application |
| CN114368745B (en) * | 2021-09-17 | 2023-11-10 | 浙江理工大学上虞工业技术研究院有限公司 | Graphene oxide, preparation method and application |
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Application publication date: 20201009 |
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