CN110255548B - Method for preparing water-dispersible graphene slurry - Google Patents
Method for preparing water-dispersible graphene slurry Download PDFInfo
- Publication number
- CN110255548B CN110255548B CN201910707392.8A CN201910707392A CN110255548B CN 110255548 B CN110255548 B CN 110255548B CN 201910707392 A CN201910707392 A CN 201910707392A CN 110255548 B CN110255548 B CN 110255548B
- Authority
- CN
- China
- Prior art keywords
- water
- graphite
- sulfonated
- graphene
- graphene slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
Abstract
The invention provides a method for preparing water-dispersible graphene slurry, which is characterized by comprising the following steps: step 1: dispersing graphite powder in water containing a dispersing agent to obtain an aqueous dispersion of the graphite powder; and 2, step: carrying out sulfonation modification on graphite powder in the graphite powder aqueous dispersion to obtain sulfonated graphite dispersion with a benzenesulfonic acid group bonded on the surface; and step 3: and mechanically stripping the sulfonated graphite dispersion liquid, and carrying out centrifugal classification to obtain the water-dispersible graphene slurry. The sulfonated graphene obtained by the invention has good water dispersibility and conductivity. Can be stored in the form of ultra-high concentration (up to 100 mg/mL) graphene aqueous slurry without secondary stacking during storage.
Description
Technical Field
The invention belongs to the technical field of stripping and dispersing preparation of graphene, and particularly relates to a method for preparing high-concentration water-dispersible graphene slurry on a large scale.
Background
In 2004, two scientists at manchester university in the united kingdom successfully prepared graphene and thus won the 2010 nobel prize. Graphene is a two-dimensional material with the thickness of only one carbon atom, and has excellent physicochemical properties. For example, the thermal conductivity coefficient of graphene is as high as 5300W/(m.K), and the current mobility under normal temperature exceeds 15000cm 2 V · s, absorption of about 2.3% over a broad wavelength range, with intensities as high as 1.0TPa. The graphene has great application prospect due to the excellent performance of the graphene.
At present, graphene in domestic and foreign markets has the problems of low productivity, high cost, difficulty in quality control, incapability of industrialization and the like. Similar to carbon nanotubes, graphene is difficult to be used as a single raw material to produce a certain product, and is mainly compounded with other material systems by utilizing the outstanding characteristics of graphene, so that a novel composite material with excellent performance is obtained. However, the problems of the dispersibility of graphene in the substrate and the compatibility of graphene with the substrate molecules need to be solved.
The preparation method of the graphene comprises the following steps: mechanical lift-off, redox, epitaxial growth, chemical vapor deposition, liquid phase lift-off, electrochemical methods, and the like. CN109354012A proposes a method for preparing graphene in large quantities at low cost, but alloy in a molten state is needed, energy is consumed when the temperature needs to reach 550-750 ℃, and the matrix alloy needs to be corroded by acid after the melt is solidified. The method of oxidation stripping of graphite is common: CN108383115A proposes a method for preparing high-quality graphene in large batch at normal temperature, and concentrated sulfuric acid and peracetic acid are used for treating graphite. However, peracetic acid is dangerous and explosive, and graphene oxide rather than graphene should be prepared; CN102167311A provides a method for preparing graphene in large batch, strong acid and strong oxidant are also used, and the graphene is obtained by reduction in an environment with the temperature of more than 300 ℃, the process is energy-consuming, and the subsequent wastewater treatment pressure is available; CN102583343A proposes a method for preparing graphene in large quantities, which can reduce expanded graphite oxide at relatively low temperature, but still cannot avoid using a large amount of strong acid and strong oxidant. CN108622888A provides a method for large-scale continuous production of graphene, graphite is subjected to dispersion and two-step mechanical stripping treatment, and the steps of strong acid, strong oxidant and high-temperature treatment are avoided. However, the used high-pressure homogenizing device needs to be provided with a cooling system separately, the equipment cost is high, and the prepared graphene has the possibility of re-agglomeration and stacking, so that the subsequent use effect is influenced.
Disclosure of Invention
The invention aims to provide a method capable of preparing water-dispersible graphene slurry with high concentration in a large scale.
In order to achieve the above object, the present invention provides a method for preparing a water-dispersible graphene slurry, comprising:
step 1: dispersing graphite powder in water containing a dispersing agent to obtain an aqueous dispersion of the graphite powder;
step 2: carrying out sulfonation modification on graphite powder in the graphite powder aqueous dispersion to obtain sulfonated graphite dispersion with a benzenesulfonic acid group bonded on the surface;
and step 3: and mechanically stripping the sulfonated graphite dispersion liquid, and carrying out centrifugal classification to obtain the water-dispersible graphene slurry.
Preferably, the dispersant is one or more of cationic dispersant, anionic dispersant, nonionic dispersant or polymer dispersant. More preferably, the dispersant is cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, polyvinyl alcohol, or a combination thereof.
Preferably, the mechanical exfoliation is high shear exfoliation or sonication, or a combination thereof.
More preferably, the high shear peeling is performed at a speed of 5000-20000rpm, the ultrasonic treatment power is 250-1000W, and the mechanical peeling time is 20-50 minutes.
Preferably, said centrifugal fractionation comprises: centrifuging at 3000-7500rpm for 10-20min to remove non-peeled multi-layer graphite flake to obtain supernatant, centrifuging or suction filtering the supernatant, washing the obtained solid, and dispersing in water to obtain water dispersible graphene slurry.
Preferably, the mass concentration of the dispersant in the water containing the dispersant is 0.2-1.5%.
Preferably, the mass ratio of the graphite to the dispersant is 1:5-1:50.
preferably, the concentration of the graphite powder aqueous dispersion is 0.1-3mg/mL.
Preferably, the sulfonated graphene contained in the water-dispersible graphene slurry has a structure in which hydrophilic groups are bonded to graphene sheets through covalent bonds.
Preferably, the sulfonated graphene contained in the water-dispersible graphene slurry can be stably dispersed in water without secondary stacking during storage.
Preferably, the concentration of sulfonated graphene contained in the water-dispersible graphene slurry can reach up to 100mg/mL.
Preferably, the conductivity of the sulfonated graphene contained in the water-dispersible graphene slurry can reach 5000S/m.
Preferably, the sulfonation modification comprises:
step 1): mixing aromatic primary amine and sodium nitrite according to the mass ratio of 1-5:1, mixing under the conditions of acid environment and ice bath, and reacting for 30-90 minutes to obtain a diazonium salt solution;
step 2): adding the diazonium salt solution obtained in the step 1) into the aqueous dispersion of graphite powder, continuously stirring under the ice bath condition, and reacting for 1-4h to obtain sulfonated graphite dispersion;
step 3): centrifuging or filtering the sulfonated graphite dispersion liquid obtained in the step 2), cleaning the obtained solid to remove redundant reactants to obtain sulfonated graphite, and dispersing the obtained sulfonated graphite in water to obtain the sulfonated graphite dispersion liquid with the surface combined with benzenesulfonic acid groups and the concentration of 0.5-5 mg/mL.
Preferably, the aromatic primary amine is one of m-aminobenzene sulfonic acid, p-aminobenzene sulfonic acid and 6-amino-1-naphthalene sulfonic acid or a combination of two or more of the m-aminobenzene sulfonic acid, the p-aminobenzene sulfonic acid and the 6-amino-1-naphthalene sulfonic acid. More preferably, the aromatic primary amine is sulfanilic acid, and the prepared sulfonated graphite has the largest concentration and the best water dispersibility after a subsequent mechanical stripping process.
Preferably, the mass ratio of the aromatic primary amine to the graphite is 1:0.35-0.53.
Compared with the prior art, the invention has the beneficial effects that:
the method avoids the problem that a large amount of strong acid and strong oxidant are needed in the common oxidation stripping process, avoids the damage to the sp2 structure of the graphene and the loss of the conductivity of the graphene in the oxidation stripping process, and simultaneously solves the problem of overlapping of the aqueous dispersion of the graphene derivative under the condition of long-term storage. The sulfonated graphene obtained by the invention has good water dispersibility and electrical conductivity. Can be stored in the form of ultra-high concentration (up to 100 mg/mL) graphene aqueous slurry without secondary stacking during storage. The method is suitable for large-scale production of the high-concentration graphene aqueous dispersion.
The method provided by the invention avoids a complex production device used in the graphene stripping process and a dangerous strong acid and strong oxidant. On the premise of environmental protection, the water-dispersible graphene is prepared, and the surface of the water-dispersible graphene contains hydrophilic groups with controllable content, so that the water-dispersible problem and the high-concentration storage problem of the graphene can be solved. The sulfonated graphene prepared by the method disclosed by the invention is thin in thickness, large in specific surface area, low in resistivity, free of metal impurities, and suitable for application in the fields of electronics, energy storage, environment, biomedical treatment, composite materials and the like.
The sulfonated graphite stripping only needs to use a mechanical stripping device commonly used in the industry, and has simple process and high yield. Due to the chemical combination of the ionized hydrophilic group and the graphene, electrostatic repulsion force and steric hindrance are introduced between adjacent graphene sheets, so that the graphene sheets cannot be stacked again in subsequent use, and the excellent performance of the graphene is influenced. Meanwhile, the sulfonated group is also beneficial to the dispersion of the sulfonated graphene in water. Compared with a common Hummers method, the method for preparing the graphene avoids conditions such as high temperature, strong acid, strong oxidant and the like, and improves the environmental protection and safety of the preparation process. In addition, compared with the traditional strong oxidation mode, the crystal defects generated by the sulfonated graphene are few, the sp2 structure damage is few, and the quality is high. Finally, the obtained high-concentration sulfonated graphene slurry can be conveniently and practically produced, transported and applied.
Drawings
Fig. 1 is an atomic force microscope morphology and lamella thickness of sulfonated graphene.
Fig. 2 is a fourier transform infrared spectrum of sulfonated graphene.
Fig. 3 is a picture of a process of adding water to redisperse sulfonated graphene powder.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Each raw material used in the following examples is a commercially available product.
Example 1
A method for preparing water-dispersible graphene slurry comprises the following specific steps:
step 1: dispersing 6g of graphite powder in 6L of aqueous dispersion containing 0.5% by mass of polyvinyl alcohol (degree of hydrolysis 88%, average molecular weight 1700), stirring to mix uniformly, and then stirring and dispersing the graphite powder dispersion at 180rpm to obtain graphite powder dispersion (1 mg/mL) which is well dispersed in the aqueous solution temporarily;
step 2: the method comprises the following steps of carrying out sulfonation modification on graphite powder in a graphite powder water dispersion liquid, and specifically comprises the following steps:
step a: adding 2.5g of sulfanilic acid and 0.76g of sodium nitrite into a sulfuric acid aqueous solution with pH =3 under the condition of ice bath at 0 ℃, and reacting for 45 minutes to obtain a diazonium salt solution;
step b: b, adding the diazonium salt solution obtained in the step a into the water dispersion of graphite powder, and continuously stirring and reacting for 3 hours at the temperature of 0 ℃ under the ice bath condition to obtain sulfonated graphite dispersion;
step c: and c, centrifuging the sulfonated graphite dispersion liquid obtained in the step b at the rotating speed of 20000rpm, washing the obtained solid with deionized water to remove redundant reactants to obtain sulfonated graphite, and dispersing the obtained sulfonated graphite in water to obtain the sulfonated graphite dispersion liquid with the surface combined with benzenesulfonic acid groups and the concentration of 3mg/mL.
And 3, step 3: mechanically stripping the sulfonated graphite dispersion by shearing at 12000rpm for 20min using a high-speed shearing disperser; then carrying out centrifugal classification, wherein the centrifugal classification comprises the following steps: centrifuging at the rotating speed of 3000rpm for 15min to remove the non-peeled multilayer graphite flakes to obtain supernatant, carrying out suction filtration on the obtained supernatant to remove redundant water, washing the obtained solid with deionized water, and dispersing in water to obtain water-dispersible graphene slurry, wherein the concentration of the water-dispersible graphene slurry is 100mg/mL, and the conductivity of the prepared sulfonated graphene is 4000S/m.
The atomic force microscopy morphology of sulfonated graphene can be seen in figure 1. The resulting sulfonated graphene sheets were approximately 1 nm thick and approximately 4 microns in diameter, demonstrating that the sulfonated graphite was exfoliated into sulfonated graphene.
Fig. 2 is a fourier transform infrared spectrum of sulfonated graphene. As can be seen in the figure, 1717 and 621cm -1 The absorption peaks at (a) correspond to the carbonyl at the edge of graphene and the C = C structure on the plane, respectively. 1160 and 1030cm -1 The absorption peak corresponds to the grafted sulfo group, 840cm -1 The absorption peaks correspond to the disubstituted phenyl structures from sodium sulfanilate, which all show that the sulfonic groups are chemically bonded to the graphene lamellae.
Fig. 3 is a picture of a process of adding water to redisperse sulfonated graphene powder. It can be seen that the water-dispersible graphene can be redispersed by deionized water within 30s without visible particles after being dried into powder. The graphene is shown to have very good hydrophilicity and dispersibility.
Example 2
A method for preparing water-dispersible graphene slurry comprises the following specific steps:
step 1: dispersing 6g of graphite powder in 6L of aqueous dispersion containing sodium dodecyl benzene sulfonate with the mass concentration of 0.8%, stirring to uniformly mix the graphite powder and the aqueous dispersion, and then stirring and dispersing the graphite powder and the aqueous dispersion at the rotating speed of 120rpm to obtain graphite powder dispersion (1 mg/mL) which is well dispersed in the aqueous solution temporarily;
step 2: the method comprises the following steps of carrying out sulfonation modification on graphite powder in a graphite powder water dispersion liquid:
step a: adding 2.9g of p-nitroaniline and 1.3g of sodium nitrite into a nitric acid aqueous solution with pH =4 under the condition of ice bath at 0 ℃, mixing, and reacting for 60 minutes to obtain a diazonium salt solution;
step b: b, adding the diazonium salt solution obtained in the step a into the aqueous dispersion of graphite powder, and continuously stirring and reacting for 2 hours under the ice bath condition of 0 ℃ to obtain sulfonated graphite dispersion;
step c: and c, centrifuging the sulfonated graphite dispersion liquid obtained in the step b at the rotating speed of 22000rpm, washing the obtained solid with deionized water to remove redundant reactants to obtain sulfonated graphite, and dispersing the obtained sulfonated graphite in water to obtain the sulfonated graphite dispersion liquid with the surface combined with benzenesulfonic acid groups and the concentration of 2 mg/mL.
And 3, step 3: mechanically stripping the sulfonated graphite dispersion liquid by shearing at 8000rpm for 50 minutes by using a high-speed shearing disperser; then carrying out centrifugal classification, wherein the centrifugal classification comprises the following steps: centrifuging at 3500rpm for 15min to remove non-peeled graphite flakes to obtain supernatant, centrifuging the obtained supernatant at 25000rpm and 60min to remove excessive water, washing the obtained solid with deionized water, and dispersing in water to obtain water-dispersible graphene slurry with concentration of 50mg/mL, wherein the conductivity of the prepared sulfonated graphene is 3300S/m.
Example 3
A method for preparing water-dispersible graphene slurry comprises the following specific steps:
step 1: dispersing 6g of graphite powder in 6L of aqueous dispersion containing 0.4% by mass of cetyltrimethylammonium bromide, stirring to mix uniformly, and then stirring and dispersing the graphite powder dispersion at a rotation speed of 150rpm to obtain graphite powder dispersion (1 mg/mL) which is well dispersed in an aqueous solution temporarily;
step 2: the method comprises the following steps of carrying out sulfonation modification on graphite powder in a graphite powder water dispersion liquid:
step a: adding 2.4g of p-aminobenzoic acid and 1.4g of sodium nitrite into hydrochloric acid aqueous solution with the pH =2 under the ice bath condition of 0 ℃, mixing, and reacting for 25 minutes to obtain diazonium salt solution;
step b: b, adding the diazonium salt solution obtained in the step a into the water dispersion of graphite powder, and continuously stirring and reacting for 2.5 hours under the ice bath condition of 0 ℃ to obtain sulfonated graphite dispersion;
step c: and c, centrifuging the sulfonated graphite dispersion liquid obtained in the step b at the rotating speed of 18000rpm, washing the obtained solid with deionized water to remove redundant reactants to obtain sulfonated graphite, and dispersing the obtained sulfonated graphite in water to obtain the sulfonated graphite dispersion liquid with the concentration of 4mg/mL and the surface combined with benzenesulfonic acid groups.
And step 3: shearing the sulfonated graphite dispersion liquid for 30 minutes at the speed of 10000rpm by using a high-speed shearing dispersion machine to perform mechanical stripping; then carrying out centrifugal classification, wherein the centrifugal classification comprises the following steps: centrifuging at the rotating speed of 4000rpm for 15min, removing the non-peeled multilayer graphite flakes to obtain supernatant, performing suction filtration on the obtained supernatant to remove redundant water, washing the obtained solid with deionized water, and dispersing in water to obtain water-dispersible graphene slurry with the concentration of 80mg/mL, wherein the conductivity of the prepared sulfonated graphene is 4250S/m.
Claims (6)
1. A method of preparing a water dispersible graphene slurry, comprising:
step 1: dispersing graphite powder in water containing a dispersing agent to obtain an aqueous dispersion of the graphite powder;
step 2: carrying out sulfonation modification on graphite powder in the graphite powder aqueous dispersion to obtain sulfonated graphite dispersion with a benzenesulfonic acid group bonded on the surface;
and 3, step 3: mechanically stripping the sulfonated graphite dispersion liquid, and carrying out centrifugal classification to obtain water-dispersible graphene slurry;
the sulfonation modification comprises the following steps:
step 1): mixing aromatic primary amine and sodium nitrite according to the mass ratio of 1-5:1, mixing under the conditions of acid environment and ice bath, and reacting for 30-90 minutes to obtain a diazonium salt solution;
step 2): adding the diazonium salt solution obtained in the step 1) into the aqueous dispersion of graphite powder, continuously stirring under the ice bath condition, and reacting for 1-4h to obtain sulfonated graphite dispersion;
step 3): centrifuging or filtering the sulfonated graphite dispersion liquid obtained in the step 2), cleaning the obtained solid to remove redundant reactants to obtain sulfonated graphite, and dispersing the obtained sulfonated graphite in water to obtain sulfonated graphite dispersion liquid with the surface combined with benzenesulfonic acid groups and the concentration of 0.5-5 mg/mL;
the aromatic primary amine is one or the combination of more than two of p-nitroaniline, p-aminobenzene sulfonic acid and p-aminobenzoic acid;
the concentration of sulfonated graphene contained in the water-dispersible graphene slurry can reach 100mg/mL at most;
the conductivity of sulfonated graphene contained in the water dispersible graphene slurry can reach 5000S/m.
2. The method for preparing the water-dispersible graphene slurry according to claim 1, wherein the dispersant is one or more of a cationic dispersant, an anionic dispersant, a nonionic dispersant or a polymeric dispersant.
3. The method of preparing a water dispersible graphene slurry according to claim 1, wherein the mechanical exfoliation is high shear exfoliation or sonication, or a combination thereof.
4. The method of preparing a water dispersible graphene slurry according to claim 1, wherein said centrifugal classification comprises: centrifuging at 3000-7500rpm for 10-20min to remove non-peeled multi-layer graphite flake to obtain supernatant, centrifuging or suction filtering the supernatant, washing the obtained solid, and dispersing in water to obtain water dispersible graphene slurry.
5. The method for preparing a water dispersible graphene slurry according to claim 1, wherein the mass concentration of the dispersant in the dispersant-containing water is 0.2-1.5%; the mass ratio of the graphite to the dispersing agent is 1:5-1:50; the concentration of the graphite powder water dispersion liquid is 0.1-3mg/mL.
6. The method for preparing water-dispersible graphene slurry according to claim 1, wherein the mass ratio of the aromatic primary amine to the graphite is 1:0.35-0.53.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910707392.8A CN110255548B (en) | 2019-08-01 | 2019-08-01 | Method for preparing water-dispersible graphene slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910707392.8A CN110255548B (en) | 2019-08-01 | 2019-08-01 | Method for preparing water-dispersible graphene slurry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110255548A CN110255548A (en) | 2019-09-20 |
| CN110255548B true CN110255548B (en) | 2023-01-17 |
Family
ID=67912662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910707392.8A Active CN110255548B (en) | 2019-08-01 | 2019-08-01 | Method for preparing water-dispersible graphene slurry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110255548B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110607167A (en) * | 2019-10-14 | 2019-12-24 | 苏州大学 | Three-dimensional composite heat dissipation slurry containing liquid metal and heat dissipation film prepared from same |
| CN112341848A (en) * | 2020-11-05 | 2021-02-09 | 上海理工大学 | Graphene coating and preparation method of graphene conductive corrosion-resistant coating |
| CN113796573B (en) * | 2021-10-09 | 2023-07-07 | 湖北中烟工业有限责任公司 | High heat conduction heating non-combustible tobacco leaf and cigarette product |
| CN114772586A (en) * | 2022-04-22 | 2022-07-22 | 浙江南烯科技有限公司 | Method for preparing high-conductivity sulfonated graphene by graphite reduction |
| CN114976001B (en) * | 2022-04-27 | 2024-03-19 | 广东一纳科技有限公司 | Composite conductive powder, preparation method thereof and lithium battery |
-
2019
- 2019-08-01 CN CN201910707392.8A patent/CN110255548B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Scalable fabrication of high quality graphene by exfoliation of edge sulfonated graphite for supercapacitor application;Ping Wen et al.;《RSC Advances》;20140725;第4卷;第35914-35918页 * |
| π-π stacking interface design for improving the strength and electromagnetic interference shielding of ultrathin and flexible water-borne polymer/sulfonated graphene composites;Linfeng Wei et al.;《Carbon》;20190423;第149卷;第679-692页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110255548A (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110255548B (en) | Method for preparing water-dispersible graphene slurry | |
| US10717652B2 (en) | Method for preparing large graphene sheets in large scale | |
| US10927009B2 (en) | Method for directly preparing expanded graphite or graphene under normal temperature and normal pressure | |
| CN106882796B (en) | Preparation method of three-dimensional graphene structure/high-quality graphene | |
| EP3190085B1 (en) | Method for preparing graphene by using high speed homogenization pretreatment and high pressure homogenization | |
| CN106672954B (en) | A kind of method of liquid phase removing preparation grapheme two-dimension material | |
| CN111591992A (en) | Single-layer MXene nanosheet and preparation method thereof | |
| CN101987729A (en) | Method for preparing graphene by reduction of sulfur-contained compound | |
| CN111320150A (en) | Method for preparing hexagonal boron nitride nanosheets by ion insertion ultrasonic stripping of alkali metal salt | |
| CN111137866A (en) | Method for preparing boron nitride nanosheet by efficiently stripping h-BN | |
| CN103408003B (en) | Method for preparing graphene | |
| CN108529573B (en) | Method for preparing hexagonal boron nitride nanosheets by using molten alkali and ultrasonic stripping technology | |
| CN108622887B (en) | Method for preparing graphene through microwave puffing | |
| CN113929089A (en) | Novel method for preparing graphene on large scale | |
| CN113443620B (en) | Preparation method and application of few-layer graphene powder | |
| CN110980707A (en) | Method for preparing few-layer graphene through mechanical stripping and few-layer graphene | |
| CN105084347A (en) | Graphene preparation method | |
| CN110921638A (en) | Method for preparing modified boron nitride nanosheet by aqueous phase shearing method | |
| KR102086764B1 (en) | Method for preparation of graphene | |
| CN109232950B (en) | High-strength high-conductivity bending-resistant graphite foil and preparation method thereof | |
| CN113233517B (en) | Single-layer/few-layer two-dimensional transition metal oxide nano material aqueous dispersion liquid and preparation method thereof | |
| KR20230090618A (en) | Method for massively manufacturing the graphene of the high quality | |
| CN111377438B (en) | Graphene and preparation method thereof | |
| CN111285361B (en) | High-performance liquid-phase mechanical preparation method of low-defect and high-dispersion graphene | |
| CN109437128A (en) | A kind of supercritical preparation process of two dimension boron nitride nanosheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |