CN112010298A - Method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide - Google Patents
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Abstract
The invention discloses a method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide, which takes natural crystalline flake graphite as a raw material and ceric sulfate (Ce (SO)4)2·4H2O), potassium permanganate (KMnO)4) Sulfuric acid (H)2SO4) Phosphorus pentoxide (P)2O5) Ammonium Nitrate (NH)4NO3) And the like as the intercalating agent and the oxidizing agent, and specifically includes the following sections. (1) Under the action of an intercalation agent, graphite fully releases interlayer space to weaken the interaction force between layers, and pre-oxidized intercalation graphite oxide is obtained; (2) oxidizing the intercalation oxide by using an oxidant to obtain a graphene oxide aggregate with a large sheet diameter; (3) and preparing the graphene oxide dispersion liquid with large sheet diameter by adopting centrifugal purification and ultrasonic stripping means. The graphene oxide prepared by the method has the characteristics of low cost of raw materials, large sheet diameter size, simple process and easiness in control, and is very suitable for industrializationAnd (4) large-scale production.
Description
Technical Field
The invention relates to the technical field of graphene material preparation, in particular to a method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide.
Background
Graphene was first prepared in 2004 by Andre k.geim (Andre k.geim) et al, university of manchester, uk, and has a number of excellent properties, for example, of grapheneThe tensile strength is up to 125GPa, the elastic modulus reaches 1.1TPa, and the theoretical specific surface area reaches 2630m2The thermal conductivity at room temperature is about 5000W/m K, etc. The excellent mechanical, thermal and electrical properties make the material become a research hotspot and show good development and application prospects in more and more industries. At present, the preparation of graphene by a redox method is considered to be an important method which is most likely to realize the industrial preparation of graphene, and the intermediate graphene oxide is an important precursor of graphene and is the most important material for realizing macroscopic assembly and modification of graphene materials. Macroscopic assembly materials that have been achieved by graphene oxide are fibers, films, aerogels, and the like.
At present, the mature methods for preparing graphene oxide mainly comprise the following three methods: (1) the Brodie method, which takes fuming nitric acid as an intercalation agent and potassium chlorate as an oxidant; (2) the Staudenmae method uses the mixture of concentrated sulfuric acid and fuming nitric acid as an intercalation agent, and uses potassium chlorate as an oxidant; (3) the Hummers method uses concentrated sulfuric acid and concentrated nitric acid as intercalation agent and potassium permanganate as oxidant. However, the graphene oxide prepared by the preparation methods has smaller sheet diameter and lower yield. Meanwhile, the preparation process has the problems of long reaction time, uneconomical consumption of reaction raw materials and incapability of large-scale preparation. The small-diameter graphene oxide greatly reduces the electric conduction, the heat conduction and the mechanical properties of the graphene macroscopic assembly material, and limits the application of the graphene oxide. Therefore, in recent years, attention has been paid to large-sheet-diameter graphene oxide and an efficient and large-scale preparation method, for example, in the application of "preparation of large-sheet graphene oxide" of chinese patent application publication No. CN103408000B, the preparation of graphite oxide by preparing layered graphite and then oxidizing is performed, and finally, the large-sheet-diameter graphene oxide is obtained by multiple times of ultrasonic dissociation; the method for preparing the large-flake-diameter graphene oxide by using natural flaky graphite, which is published in Chinese invention patent No. CN104556021A, is characterized in that the large-flake-diameter graphene oxide is obtained by preparing the graphite oxide and stripping and dispersing the graphite oxide by using a high-speed dispersion homogenizer; the method for preparing fragment-free super-large graphene oxide sheets, which is published in the Chinese patent application No. CN105692599A, prepares graphene oxide by a Modified-Hummer method, and finally prepares a graphene oxide dispersion liquid by stripping through a shaking table. Although the three patents have better technical ideas, the defects of longer reaction time, complex process and the like still exist, and the control of the product quality and the large-scale production are not facilitated.
In conclusion, in the aspect of graphene oxide preparation, an effective optimization mechanism is explored, the rapid, economic and environment-friendly macro-preparation of the graphene oxide with the hundred-micron-level ultra-large sheet diameter is realized, and the method has important significance and value for the deep development of the graphene macro-body functional material.
Disclosure of Invention
Based on the defects, the invention aims to provide the method for rapidly, efficiently and massively preparing the large-sheet-diameter graphene oxide, the method has the advantages of simple and rapid operation process, low production cost, no need of special production equipment and the like, and the pollution of an oxidant to the environment is weakened to a certain extent.
The technical method adopted by the invention comprises the following steps:
(1) adding flake graphite into an intercalation agent (concentrated sulfuric acid, ammonium nitrate and ceric sulfate) to obtain an intercalation graphite oxide, pouring the reaction solution into deionized water, washing with water for four times, and filtering with a 120-mesh screen to obtain a filtered product;
(2) adding the dried intercalated graphite oxide into a mixed solution of concentrated sulfuric acid, phosphorus pentoxide and potassium permanganate to carry out stirring oxidation reaction;
(3) pouring the mixed solution treated in the step (2) into ice water, adding a certain amount of hydrogen peroxide (the solution turns golden yellow), adding concentrated hydrochloric acid (the concentration is 12mo1/L) until flocculent graphene oxide aggregates disappear, and then cleaning for three times;
(4) and (4) centrifugally purifying the graphene oxide aggregate obtained in the step (3), and finally performing ultrasonic-assisted treatment to obtain the large-sheet-diameter graphene oxide.
Further, the diameter of the flake graphite sheet in the step (1) is 300-500 um.
Further, the intercalated oxide in the step (1) is prepared by the following method: fully dissolving ceric sulfate and ammonium nitrate in concentrated sulfuric acid with the mass fraction of 98%, adding graphite, stirring for 3min, stopping stirring, and stirring and reacting for 60-70 min at 75-80 ℃ in a water bath to obtain graphite oxide with full intercalation; the mass volume ratio of the graphite to the ammonium nitrate to the ceric sulfate to the concentrated sulfuric acid is 3g to 1.5g to 20m 1.
Further, the mass volume ratio of the graphite to the deionized water in the step (1) is 1g:300 ml.
Further, the filter screen in the step (1) is an acid-resistant screen such as titanium alloy.
Further, the oxidation reaction method in the step (2) specifically comprises the following steps: at normal temperature, fully dissolving phosphorus pentoxide and potassium permanganate in 98% concentrated sulfuric acid by mass fraction, adding dried intercalated graphite oxide, stirring for 2min, and reacting at 50-55 ℃ for 3.5-5h to obtain graphene oxide agglomerate reaction liquid; the intercalation graphite oxide: concentrated sulfuric acid: phosphorus pentoxide: the mass volume ratio of the potassium permanganate is 1g to 50ml to 1.5g to 2 g.
Further, the washing method in the step (3) is as follows: pouring the reaction liquid into an ice-water mixture, wherein the mass ratio of ice to water in the ice-water mixture is 1: 3; (ii) a The volume ratio of the reaction liquid to water is 1: 6; uniformly stirring, adding 30% of hydrogen peroxide by mass, wherein the volume ratio of hydrogen peroxide to the reaction liquid is 1:20, the volume ratio of hydrochloric acid to deionized water is 1:10, pouring out supernatant after precipitation, and washing for 3 times in sequence by using hydrochloric acid.
Further, in the step (4), the centrifugal purification times are 3 times, the mass volume ratio of the crystalline flake graphite used for centrifugation to water is 1g:400ml, a cell crusher is adopted for auxiliary stripping, the ultrasonic power is 200-260W, and the ultrasonic time is about 2-3 hours.
The invention belongs to the technical field of graphene oxide and graphene preparation, and relates to a method for preparing large-sheet-diameter graphene oxide with high efficiency and low consumption.
Has the advantages that:
1. the graphene oxide prepared by the technology has the advantages of large sheet diameter size, good oxidation effect, uniform structure, yield close to 100 percent and high single-layer rate;
2. the preparation process is simple, expensive special equipment is not needed, high-temperature expansion conditions such as a microwave reactor and a high-temperature furnace are not needed, and the complex process flow of thermal expansion is avoided;
3. compared with the traditional graphene oxide preparation method, the method has the advantages of short reaction time, mild reaction conditions, low energy consumption, low production cost, high efficiency and low consumption of oxidant, so that the pollution to the environment is reduced;
4. the graphene oxide and graphene sheet layer sizes prepared by the method are larger than those of samples or products prepared by most of the methods disclosed or reported in the prior art.
Detailed Description
Example 1
A method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide comprises the following steps:
(1) adding flake graphite into an intercalation agent consisting of concentrated sulfuric acid, ammonium nitrate and ceric sulfate to obtain an intercalation graphite oxide, pouring the reaction solution into deionized water, repeatedly washing for four times, and filtering on a 120-mesh screen to obtain a filtered product;
(2) adding the dried intercalated graphite oxide into a mixed solution of concentrated sulfuric acid, phosphorus pentoxide and potassium permanganate, and stirring for oxidation reaction;
(3) pouring the mixed solution treated in the step (2) into an ice-water mixture, adding a certain amount of hydrogen peroxide until the solution turns golden yellow, adding concentrated hydrochloric acid with the concentration of 12mo1/L until flocculent graphene oxide aggregates disappear, and then cleaning for three times;
(4) and (4) centrifugally purifying the graphene oxide aggregate obtained in the step (3), and finally carrying out ultrasonic-assisted treatment to obtain large graphene oxide sheets.
The particle size of the flake graphite in the step (1) is 300 um.
The intercalation oxide in the step (1) is prepared by the following method: fully dissolving ceric sulfate and ammonium nitrate in 98% concentrated sulfuric acid by mass fraction, adding graphite, stirring for 3min, stopping stirring, placing the mixed solution in a water bath, and stirring and reacting at 75 ℃ for 60min to obtain graphite oxide with full intercalation; the mass volume ratio of the graphite to the ammonium nitrate to the ceric sulfate to the concentrated sulfuric acid is 3g to 1.5g to 20m 1.
The mass volume ratio of the graphite to the deionized water in the step (1) is 1g to 300 ml.
The filter screen in the step (1) is an acid-resistant screen such as a titanium alloy screen.
The oxidation reaction method in the step (2) specifically comprises the following steps: at normal temperature, fully dissolving phosphorus pentoxide and potassium permanganate in 98% concentrated sulfuric acid by mass fraction, adding dried intercalated graphite oxide, stirring for 2min, and reacting at 50 ℃ for 3.5 hours to obtain graphene oxide agglomerate reaction liquid; the intercalation graphite oxide: concentrated sulfuric acid: phosphorus pentoxide: the mass volume ratio of the potassium permanganate is 1g to 50ml to 1.5g to 2 g.
The washing method in the step (3) is as follows: pouring the reaction liquid into ice water, wherein the volume ratio of the reaction liquid to the water is 1: 6; uniformly stirring, adding 30% of hydrogen peroxide by mass, wherein the volume ratio of hydrogen peroxide to the reaction liquid is 1:20, the volume ratio of hydrochloric acid to deionized water is 1:10, pouring out supernatant after precipitation, and washing for 3 times in sequence by using hydrochloric acid.
In the step (4), the centrifugal purification times are 3 times, the mass volume ratio of the flake graphite used for centrifugation to water is 1g:400ml, a cell crusher is adopted for auxiliary stripping, the ultrasonic power is 200W, and the ultrasonic time is about 2 hours.
Example 2
A method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide comprises the following steps:
(1) adding flake graphite into an intercalation agent consisting of concentrated sulfuric acid, ammonium nitrate and ceric sulfate to obtain an intercalation graphite oxide, pouring the reaction solution into deionized water, repeatedly washing for four times, and filtering on a 120-mesh screen to obtain a filtered product;
(2) adding the dried intercalated graphite oxide into a mixed solution of concentrated sulfuric acid, phosphorus pentoxide and potassium permanganate, and stirring for oxidation reaction;
(3) pouring the mixed solution treated in the step (2) into an ice-water mixture, adding a certain amount of hydrogen peroxide until the solution turns golden yellow, adding concentrated hydrochloric acid with the concentration of 12mo1/L until flocculent graphene oxide aggregates disappear, and then cleaning for three times;
(4) and (4) centrifugally purifying the graphene oxide aggregate obtained in the step (3), and finally carrying out ultrasonic-assisted treatment to obtain large graphene oxide sheets.
The particle size of the flake graphite in the step (1) is 400 um.
The intercalation oxide in the step (1) is prepared by the following method: fully dissolving ceric sulfate and ammonium nitrate in concentrated sulfuric acid with the mass fraction of 98%, adding graphite, stirring for 3min, stopping stirring, placing the mixed solution in a water bath, and stirring and reacting at 78 ℃ for 65min to obtain graphite oxide with full intercalation; the mass volume ratio of the graphite to the ammonium nitrate to the ceric sulfate to the concentrated sulfuric acid is 3g to 1.5g to 20m 1.
The mass volume ratio of the graphite to the deionized water in the step (1) is 1g to 300 ml.
The filter screen in the step (1) is an acid-resistant screen such as a titanium alloy screen.
The oxidation reaction method in the step (2) specifically comprises the following steps: at normal temperature, fully dissolving phosphorus pentoxide and potassium permanganate in 98% concentrated sulfuric acid by mass fraction, adding dried intercalated graphite oxide, stirring for 2min, and reacting at 52 ℃ for 4.2h to obtain graphene oxide agglomerate reaction liquid; the intercalation graphite oxide: concentrated sulfuric acid: phosphorus pentoxide: the mass volume ratio of the potassium permanganate is 1g to 50ml to 1.5g to 2 g.
The washing method in the step (3) is as follows: pouring the reaction liquid into ice water, wherein the volume ratio of the reaction liquid to the water is 1: 6; uniformly stirring, adding 30% of hydrogen peroxide by mass, wherein the volume ratio of hydrogen peroxide to the reaction liquid is 1:20, the volume ratio of hydrochloric acid to deionized water is 1:10, pouring out supernatant after precipitation, and washing for 3 times in sequence by using hydrochloric acid.
In the step (4), the centrifugal purification times are 3 times, the mass volume ratio of the flake graphite used for centrifugation to water is 1g:400ml, a cell crusher is adopted for auxiliary stripping, the ultrasonic power is 240W, and the ultrasonic time is about 2.5 hours.
Example 3
A method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide comprises the following steps:
(1) adding flake graphite into an intercalation agent consisting of concentrated sulfuric acid, ammonium nitrate and ceric sulfate to obtain an intercalation graphite oxide, pouring the reaction solution into deionized water, repeatedly washing for four times, and filtering on a 120-mesh screen to obtain a filtered product;
(2) adding the pressed intercalated graphite oxide into a mixed solution of concentrated sulfuric acid, phosphorus pentoxide and potassium permanganate for stirring oxidation reaction;
(3) pouring the mixed solution treated in the step (2) into an ice-water mixture, adding a certain amount of hydrogen peroxide until the solution turns golden yellow, adding concentrated hydrochloric acid with the concentration of 12mo1/L until flocculent graphene oxide aggregates disappear, and then cleaning for three times;
(4) and (4) centrifugally purifying the graphene oxide aggregate obtained in the step (3), and finally carrying out ultrasonic-assisted treatment to obtain large graphene oxide sheets.
The particle size of the flake graphite in the step (1) is 500 um.
The intercalation oxide in the step (1) is prepared by the following method: fully dissolving ceric sulfate and ammonium nitrate in 98% concentrated sulfuric acid by mass fraction, adding graphite, stirring for 3min, stopping stirring, placing the mixed solution in a water bath, and stirring and reacting at 80 ℃ for 70min to obtain graphite oxide with full intercalation; the mass volume ratio of the graphite to the ammonium nitrate to the ceric sulfate to the concentrated sulfuric acid is 3g to 1.5g to 20m 1.
The mass volume ratio of the graphite to the deionized water in the step (1) is 1g to 300 ml.
The filter screen in the step (1) is an acid-resistant screen such as a titanium alloy screen.
The oxidation reaction method in the step (2) specifically comprises the following steps: at normal temperature, fully dissolving phosphorus pentoxide and potassium permanganate in 98% concentrated sulfuric acid by mass fraction, adding dried intercalated graphite oxide, stirring for 2min, and then reacting at 55 ℃ for 5h to obtain graphene oxide agglomerate reaction liquid; the intercalation graphite oxide: concentrated sulfuric acid: phosphorus pentoxide: the mass volume ratio of the potassium permanganate is 1g to 50ml to 1.5g to 2 g.
The washing method in the step (3) is as follows: pouring the reaction liquid into ice water, wherein the volume ratio of the reaction liquid to the water is 1: 6; uniformly stirring, adding 30% of hydrogen peroxide by mass, wherein the volume ratio of hydrogen peroxide to the reaction liquid is 1:20, the volume ratio of hydrochloric acid to deionized water is 1:10, pouring out supernatant after precipitation, and washing for 3 times in sequence by using hydrochloric acid.
In the step (4), the centrifugal purification times are 3 times, the mass volume ratio of the crystalline flake graphite used for centrifugation to water is 1g:400ml, a cell crusher is adopted for auxiliary stripping, the ultrasonic power is 260W, and the ultrasonic time is about 3 hours.
The invention relates to the technical field of graphene material preparation, and discloses a method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide. Natural flake graphite is used as raw material, ceric sulfate (Ce (SO)4)2·4H2O), potassium permanganate (KMnO)4) Sulfuric acid (H)2SO4) Phosphorus pentoxide (P)2O5) Ammonium Nitrate (NH)4NO3) And the like as the intercalating agent and the oxidizing agent, and specifically includes the following sections. (1) Under the action of an intercalation agent, graphite fully releases interlayer space to weaken the interaction force between layers, and pre-oxidized intercalation graphite oxide is obtained; (2) oxidizing the intercalation oxide by using an oxidant to obtain a graphene oxide aggregate with a large sheet diameter; (3) and preparing the graphene oxide dispersion liquid with large sheet diameter by adopting centrifugal purification and ultrasonic stripping means. The graphene oxide prepared by the method has the characteristics of cheap raw materials, large sheet diameter size, simple process and easiness in control, and is very suitable for industrial large-scale production.
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 (8)
1. A method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide is characterized by comprising the following steps: the method comprises the following steps:
(1) adding flake graphite into an intercalation agent consisting of concentrated sulfuric acid, ammonium nitrate and ceric sulfate to obtain an intercalation graphite oxide, pouring the reaction solution into deionized water, washing for four times, and filtering on a 120-mesh screen to obtain a filtered product;
(2) adding the dried intercalated graphite oxide into a mixed solution of concentrated sulfuric acid, phosphorus pentoxide and potassium permanganate, and fully stirring for oxidation reaction;
(3) slowly pouring the mixed solution obtained by the reaction in the step (2) into an ice water mixture, adding a certain amount of hydrogen peroxide until the solution turns golden yellow, adding concentrated hydrochloric acid with the concentration of 12mo1/L until flocculent graphene oxide aggregates disappear, and then cleaning for three times;
(4) and (4) centrifugally purifying the graphene oxide aggregate obtained in the step (3), and finally carrying out ultrasonic-assisted treatment to obtain large graphene oxide sheets.
2. The method for rapidly, efficiently and massively preparing the large-sheet-size graphene oxide according to claim 1, wherein the method comprises the following steps:
the particle size of the crystalline flake graphite in the step (1) is 300-500 um.
3. The method for rapidly, efficiently and massively preparing the large-sheet-size graphene oxide according to claim 1, wherein the method comprises the following steps:
the intercalation oxide in the step (1) is prepared by the following method: fully dissolving ceric sulfate and ammonium nitrate in concentrated sulfuric acid with the mass fraction of 98%, adding graphite, stirring for 3min, stopping stirring, placing the mixed solution in a water bath, and stirring and reacting at 75-80 ℃ for 60-70 min to obtain graphite oxide with full intercalation; the mass volume ratio of the graphite to the ammonium nitrate to the ceric sulfate to the concentrated sulfuric acid is 3g to 1.5g to 20m 1.
4. The method for rapidly, efficiently and massively preparing the large-sheet-size graphene oxide according to claim 1, wherein the method comprises the following steps:
the mass volume ratio of the graphite to the deionized water in the step (1) is 1g to 300 ml.
5. The method for rapidly, efficiently and massively preparing the large-sheet-size graphene oxide according to claim 1, wherein the method comprises the following steps:
the filter screen in the step (1) is an acid-resistant screen such as a titanium alloy screen.
6. The method for rapidly, efficiently and massively preparing the large-sheet-size graphene oxide according to claim 1, wherein the method comprises the following steps:
the oxidation reaction method in the step (2) specifically comprises the following steps: at normal temperature, fully dissolving phosphorus pentoxide and potassium permanganate in 98% concentrated sulfuric acid by mass fraction, adding dried intercalated graphite oxide, stirring for 2min, and reacting at 50-55 ℃ for 3.5-5h to obtain graphene oxide agglomerate reaction liquid; the intercalation graphite oxide: concentrated sulfuric acid: phosphorus pentoxide: the mass volume ratio of the potassium permanganate is 1g to 50ml to 1.5g to 2 g.
7. The method for rapidly, efficiently and massively preparing the large-sheet-size graphene oxide according to claim 1, wherein the method comprises the following steps:
the washing method in the step (3) is as follows: pouring the reaction liquid into an ice-water mixture, wherein the mass ratio of the ice-water mixture is 1:3, and the volume ratio of the reaction liquid to the ice-water mixture is 1: 6; stirring uniformly, adding 30% of hydrogen peroxide by mass, wherein the volume ratio of hydrogen peroxide to the reaction liquid is 1:20, the volume ratio of hydrochloric acid to deionized water is 1:10, precipitating, pouring out the supernatant, and washing for 3 times by using hydrochloric acid.
8. The method for rapidly, efficiently and massively preparing the large-sheet-size graphene oxide according to claim 1, wherein the method comprises the following steps:
in the step (4), the centrifugal purification times are 3 times, the mass volume ratio of the crystalline flake graphite used for centrifugation to water is 1g:400ml, a cell crusher is adopted for auxiliary stripping, the ultrasonic power is 200-260W, and the ultrasonic time is about 2-3 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112794705A (en) * | 2021-01-13 | 2021-05-14 | 兰州大学 | Method for preparing hyperelastic silicon oxide nano ceramic aerogel based on graphene serving as template |
| CN113213469A (en) * | 2021-05-31 | 2021-08-06 | 杭州高烯科技有限公司 | Equipment for preparing uniform small-size graphene oxide |
| CN114031073A (en) * | 2021-09-22 | 2022-02-11 | 广东墨睿科技有限公司 | Method for macroscopic preparation of graphene oxide with complete and uniform size and ultra-large sheet diameter |
| RU2783099C2 (en) * | 2021-03-24 | 2022-11-08 | ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ "РОССИЙСКИЙ НАУЧНЫЙ ЦЕНТР РАДИОЛОГИИ И ХИРУРГИЧЕСКИХ ТЕХНОЛОГИЙ ИМЕНИ АКАДЕМИКА А.М. ГРАНОВА" МИНИСТЕРСТВА ЗДРАВООХРАНЕНИЯ РОССИЙСКОЙ ФЕДЕРАЦИИ / ФГБУ "РНЦРХТ им. академика А.М. Гранова" Минздрава России | Method for scaling synthesis of graphene oxide |
| CN115849359A (en) * | 2022-11-28 | 2023-03-28 | 内蒙古大学 | Preparation method of single-layer graphene oxide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452650A (en) * | 2010-10-27 | 2012-05-16 | 清华大学 | Process for preparing graphene by cryochemical method |
| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| CN102674336A (en) * | 2012-06-01 | 2012-09-19 | 南京大学 | Phosphorylcholine structure-modified graphene oxide and preparation method thereof |
| US20130153855A1 (en) * | 2011-12-16 | 2013-06-20 | International Business Machines Corporation | Chemical Oxidation of Graphene and Carbon Nanotubes Using Cerium (IV) Ammonium Nitrate |
| US20130153831A1 (en) * | 2011-12-16 | 2013-06-20 | International Business Machines Corporation | Cerium (IV) Salts as Effective Dopant for Carbon Nanotubes and Graphene |
| CN103408000A (en) * | 2013-07-25 | 2013-11-27 | 黑龙江科技大学 | Preparation method for oxidized grapheme in large sheet |
| CN105692599A (en) * | 2016-01-25 | 2016-06-22 | 浙江碳谷上希材料科技有限公司 | Preparation method of fragment-free super-large graphene oxide sheet |
-
2020
- 2020-08-14 CN CN202010820163.XA patent/CN112010298A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452650A (en) * | 2010-10-27 | 2012-05-16 | 清华大学 | Process for preparing graphene by cryochemical method |
| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| US20130153855A1 (en) * | 2011-12-16 | 2013-06-20 | International Business Machines Corporation | Chemical Oxidation of Graphene and Carbon Nanotubes Using Cerium (IV) Ammonium Nitrate |
| US20130153831A1 (en) * | 2011-12-16 | 2013-06-20 | International Business Machines Corporation | Cerium (IV) Salts as Effective Dopant for Carbon Nanotubes and Graphene |
| CN102674336A (en) * | 2012-06-01 | 2012-09-19 | 南京大学 | Phosphorylcholine structure-modified graphene oxide and preparation method thereof |
| CN103408000A (en) * | 2013-07-25 | 2013-11-27 | 黑龙江科技大学 | Preparation method for oxidized grapheme in large sheet |
| CN105692599A (en) * | 2016-01-25 | 2016-06-22 | 浙江碳谷上希材料科技有限公司 | Preparation method of fragment-free super-large graphene oxide sheet |
Non-Patent Citations (3)
| Title |
|---|
| MINQIANG SUN ET AL.: "Rational synthesis of novel π-conjugated poly(1,5-diaminoanthraquinone) for high-performance supercapacitors", 《RSC ADVANCES》 * |
| 周晓 等: "石墨烯负载新型π-共轭聚合物纳米复合电极材料的合成及其超级电容特性", 《物理化学学报》 * |
| 张宝强: "基于石墨烯薄膜的自发热路面融雪化冰研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅱ辑》 * |
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| RU2783099C2 (en) * | 2021-03-24 | 2022-11-08 | ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ "РОССИЙСКИЙ НАУЧНЫЙ ЦЕНТР РАДИОЛОГИИ И ХИРУРГИЧЕСКИХ ТЕХНОЛОГИЙ ИМЕНИ АКАДЕМИКА А.М. ГРАНОВА" МИНИСТЕРСТВА ЗДРАВООХРАНЕНИЯ РОССИЙСКОЙ ФЕДЕРАЦИИ / ФГБУ "РНЦРХТ им. академика А.М. Гранова" Минздрава России | Method for scaling synthesis of graphene oxide |
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