CN103408000A - Preparation method for oxidized grapheme in large sheet - Google Patents
Preparation method for oxidized grapheme in large sheet Download PDFInfo
- Publication number
- CN103408000A CN103408000A CN2013103172842A CN201310317284A CN103408000A CN 103408000 A CN103408000 A CN 103408000A CN 2013103172842 A CN2013103172842 A CN 2013103172842A CN 201310317284 A CN201310317284 A CN 201310317284A CN 103408000 A CN103408000 A CN 103408000A
- Authority
- CN
- China
- Prior art keywords
- acid
- graphite
- mixing
- hydrogen peroxide
- nitric acid
- 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.)
- Granted
Links
Images
Abstract
The invention relates to a preparation method for oxidized graphene in a large sheet. The method comprises the following steps: uniformly mixing natural scale graphite with the mixed acid of concentrated nitric acid or nitric acid and sulfuric acid in a reactor; adding hydrogen peroxide from the bottom of the reactor; reacting under mixing for 10-60 min; washing with water and drying to obtain layered graphite; mixing the layered graphite with strong acid; adding strong oxidant slowly; performing ultrasound-assisted oxidation reaction in an ice-water bath for 30-60 min after uniform mixing; heating the reaction mixture to 50-60 DEG C and continuing mixing for 6-12 h; adding deionized water and performing ultrasound-assisted mixing reaction for 10-30 min; cleaning the obtained product first with mixed solution of diluted hydrochloric acid and hydrogen perhydrol, then with deionized water; performing centrifugal separation to obtain oxidized graphene. The method provided by the invention is simple in operation, high in oxidation efficiency and free from environment pollution; the prepared oxidized graphene has a high peeling rate and a high specific surface area.
Description
Technical field
The present invention relates to a kind of preparation method of graphene oxide, particularly relate to a kind of preparation method of large stretch of graphene oxide.
Background technology
Since the A.K.Geim group of Univ Manchester UK in 2004 prepared Graphene by the method for mechanically peel graphite first, Graphene, as a kind of novel two-dimensional nano carbonaceous material, because it has unique structure and performance, enjoyed people's concern.A kind of cellular two-dirnentional structure material of hexagonal lattice formed with the sp2 hybridized orbital by carbon atom of Graphene, thickness in monolayer is 0.35nm, C-C bond distance is 0.142nm, is the elementary cell that forms soccerballene, carbon nanotube and graphite, has the performances such as excellent conduction, heat conduction, mechanics and electrochemistry.The theoretical specific surface area of monoatomic layer grapheme material is up to 2630m
2/ g, semi-conductor intrinsic electronic mobility is about 2 * 10
5Cm
2/ Vs, resistivity is about 10
-6Ω cm, thermal conductivity is up to 5000W/mK, and Young's modulus is 1100GPa, and breaking tenacity is 125GPa, and transmittance is up to 97.7%.Based on above-mentioned characteristic, Graphene has boundless application prospect in fields such as electronics, information, the energy, biology, medical science.
The main preparation methods of Graphene has micromechanics stripping method, epitaxial growth method, chemical Vapor deposition process, oxidation reduction process, liquid phase stripping method etc. both at home and abroad.Oxidation reduction process is at present comparatively common low cost, the method for preparing efficiently big area thin layer graphite alkene material.The method is carried out oxidation by high-purity natural graphite by oxidation technology, obtain basic molecular structure and be the graphene oxide of the groups such as a large amount of hydroxyl of C hexagon and surface and marginal existence, carboxyl, epoxy, graphene oxide is washed to neutrality, by the method for reduction, remove the oxy radical on its molecular structure again, finally obtain the method for grapheme material.In the standby technique of the chemistry redox legal system of Graphene, the technology of preparing of large stretch of oxide thin layer Graphene is particularly crucial.The method for oxidation of graphite mainly contains Brodie, Staudenmaier and tri-kinds of methods of Hummers.Brodie method graphite and NaClO
4In beaker, fully mix, in ice bath, add dense HNO
3, after mixing, mixture is heated to 60 ℃, continue to stir 24h, the oxidation graphite solid of then filtering gained, the HCI solution with 5% cleans, and filters, then dry.The degree of oxidation of the graphite oxide obtained after washing is lower, need carry out repeatedly oxide treatment to improve degree of oxidation, and the reaction times is relatively long.The advantage of the method is that its degree of oxidation can utilize oxidization time to control, and synthetic graphite oxide crystallinity is high.But because adopting perchlorate to make oxygenant, danger is larger, and can produce more toxic gas in reaction process.The Staudenmaier method is to adopt vitriol oil system, and perchlorate and nitrosonitric acid are oxygenant, and the temperature of reaction system need to maintain 0 ℃ always.Degree of oxidation increases with the increase in reaction times, can control the final degree of oxidation of graphite by controlling the reaction times.Its shortcoming is that the reaction times is longer, and degree of oxidation is lower, need carry out repeatedly oxide treatment, in the XRD figure of resulting product, the graphite diffraction peak just do not occur after general oxidation 56h.In addition, the toxic gas substance C l produced in reaction process
2More.The Hummers method is to adopt the vitriol oil and nitrate system, and the permanganate of take is oxygenant, prepares graphite oxide through low temperature (below 4 ℃), middle temperature (35 ℃ of left and right) and three step of reaction of high temperature (below 98 ℃).The oxidization time of the method is shorter, and the degree of oxidation of product is higher, and the crystalline structure of product is more regular, and is easy to swelling occur and leafing in water.At present, there have been the graphite microparticles of take or expanded graphite to be raw material, adopt the patent report of the standby graphene oxide of improved Hummers legal system, yet take the small grain size graphite microparticles during as raw material, its oxidation efficiency is higher, take flaky graphite during as raw material, and the peelable degree of its oxidation efficiency and graphite oxide is all poor; Take expanded graphite during as raw material, quasiflake graphite after although expand provides more contact area for strong acid and strong oxidizer, improved oxidation efficiency, yet the huge expanding volume of expanded graphite makes oxidizing reaction need more acid, in addition, at high temperature puffing, prepare in the expanded graphite process, energy consumption is higher, and sulfide or the nitride of release cause severe contamination to environment.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the invention provides a kind of preparation method of large stretch of graphene oxide, at first this preparation method carries out pre-treatment to graphite to prepare exfoliated graphite, then adopts ultrasonic assisted oxidation reaction to prepare graphene oxide.The method is simple to operate, and oxidation efficiency is high, non-environmental-pollution, and the graphene oxide degree of peeling off of preparation is high, and specific surface area is large.
For reaching above-mentioned purpose, the preparation method of a kind of large stretch of graphene oxide of the present invention, it comprises the following steps:
(1) in reactor, natural flake graphite is mixed with the mixing acid of concentrated nitric acid or nitric acid and sulfuric acid composition, from reactor bottom, add hydrogen peroxide (if add from top, hydrogen peroxide easily decomposes, be unfavorable for the carrying out reacted), stirring reaction 10-60min, obtain exfoliated graphite after washing, drying;
(2) exfoliated graphite is mixed with strong acid, slowly adds strong oxidizer, after mixing in ice-water bath ultrasonic assisted oxidation reaction 30-60min;
(3) reaction mixture of step (2) is warming up to 50-60 ℃ and the lasting 6-12h of stirring, add the ultrasonic auxiliary lower stirring reaction 10-30min of deionized water (preferably the ratio of exfoliated graphite and deionized water is 1g:100mL), products therefrom first cleans with the mixing solutions of dilute hydrochloric acid and hydrogen peroxide, and then use washed with de-ionized water, centrifugation, obtain graphene oxide.
Graphite raw material purity is more high better, but the cost of high purity graphite raw material is higher.The existing method general requirement raw material for preparing Graphene is high purity graphite, and the inventive method is not limited to the high purity graphite raw material, also very applicable for non-high purity graphite raw material.The granularity of graphite raw material is the smaller the better, and granularity is larger, and oxidation efficiency is lower, and granularity is less, and oxidation efficiency is high, but the graphene sheet layer obtained is less.So the present invention does not require purity and the granularity of graphite, but the angle reduced production costs from enhancing productivity, preferably the purity of graphite is 75-99.9%, granularity is 150-270 μ m.
Method of the present invention, wherein natural flake graphite in preferred described step (1): the mixing acid of concentrated nitric acid or nitric acid and sulfuric acid: hydrogen peroxide=1g:3-5mL:0.5-1mL.
Method of the present invention, wherein in preferred described mixing acid, the volume ratio of nitric acid and sulfuric acid is (8-9): 1.
Method of the present invention, wherein preferred described concentration of nitric acid is the 85%(mass percent), sulfuric acid concentration is the 98%(mass percent), hydrogen peroxide concentration is the 60%(mass percent).
Method of the present invention, wherein in preferred described step (2), ultrasonic assisted oxidation reaction strong acid used is the mixing acid that mix with arbitrary proportion the vitriol oil, concentrated nitric acid, perchloric acid or they, and strong oxidizer is the mixture that mix with arbitrary proportion potassium permanganate, SODIUMNITRATE, potassium bichromate, saltpetre or they.
Method of the present invention, wherein in preferred described step (2), the ratio of exfoliated graphite and strong acid is 1g:25-50mL, the part by weight of exfoliated graphite and strong oxidizer is 1:(3-5), concrete ratio is determined according to the granularity of exfoliated graphite, the granularity of exfoliated graphite is larger, and required strong acid and the amount of strong oxidizer are just larger.
Method of the present invention, wherein in preferred described step (2) and step (3), the ultrasonic power of ultrasonic assisted oxidation reaction is 40-50kHz.
Method of the present invention, wherein the mixing solutions of dilute hydrochloric acid and hydrogen peroxide is to be that 10% dilute hydrochloric acid and mass percent are that 1% hydrogen peroxide is mixed to get with volume ratio 1:1 by mass percent in preferred described step (3).
The invention still further relates to the graphene oxide obtained by aforesaid method.
Difference from prior art is, at first the present invention prepares exfoliated graphite by the intercalation that hydrogen peroxide replaces solid oxidizing agent, then adopts ultrasonic assisted oxidation reaction to prepare graphene oxide.Not only can greatly improve the oxidation efficiency of graphite, and ultrasonic assisted reaction makes the graphite oxide prepared without peeling off, the Graphene degree of peeling off of preparation is high, and specific surface area is large.The present invention prepares the method for graphene oxide, simple to operate, reduces energy consumption, non-environmental-pollution.
Preparation method to large stretch of graphene oxide of the present invention is described further below in conjunction with accompanying drawing.
The accompanying drawing explanation
Fig. 1 is that the SEM of the exfoliated graphite that makes of example 1 of the present invention characterizes photo;
Fig. 2 is that the XRD of the exfoliated graphite that makes of example 1 of the present invention and graphite oxide characterizes spectrogram;
Fig. 3 is that the FTIR of the graphite oxide that makes of example 1 of the present invention characterizes spectrogram;
Fig. 4 is that the TEM of the graphene oxide that makes of example 1 of the present invention characterizes photo;
Fig. 5 is that the TEM of the graphene oxide that makes of example 2 of the present invention characterizes photo;
Fig. 6 is that the TEM of the graphene oxide that makes of example 3 of the present invention characterizes photo.
Embodiment
Be below embodiment and testing data thereof etc., but content of the present invention is not limited to the scope of these embodiment.
By 10g purity, be that 99% granularity is that the natural flake graphite of 150 μ m mixes with the 30mL concentrated nitric acid, from reactor bottom, adding the concentration of 5mL is 60% hydrogen peroxide, stirring reaction 20min, and washing, obtain exfoliated graphite after drying; Take the 2g exfoliated graphite and mix with the vitriol oil of 80mL, slowly add 6g potassium permanganate, after mixing in ice-water bath ultrasonic assisted oxidation reaction 30min, ultrasonic power is 40kHz; Mixture is warming up to 50 ℃ and the lasting 10h of stirring, add the ultrasonic auxiliary lower stirring reaction 20min of 200mL deionized water, products therefrom is first used the 10%(mass percent) dilute hydrochloric acid and 1%(mass percent) hydrogen peroxide mixed solution carries out eccentric cleaning with volume ratio 1:1, and then use washed with de-ionized water, centrifugation, obtain graphene oxide.
The SEM of the exfoliated graphite obtained by the present embodiment characterizes and (adopts the MX2600FE scanning electronic microscope, Britain Camscan company.Dry exfoliated graphite powder is evenly adhered on conductive tape and directly tests) with reference to accompanying drawing 1, as can be seen from Figure 1 after the acidified oxidation pre-treatment of natural flake graphite, the part graphite flake layer is stripped from out, present flower-shaped graphite-structure, this structure graphite specific surface area is larger, is conducive to the further oxidation of graphite.
The XRD of exfoliated graphite and graphite oxide characterizes and (adopts German D8Advance type diffractometer to carry out the XRD sign to material.X-ray source be Cu – K alpha-ray (electric current 40mA, sweep limit 2 θ are between 5 °～70 ° for λ=0.15406nm), voltage 40kV, 6 °/min of sweep velocity, 0.02 ° of scanning step, detector are scintillometer.The graphene oxide sample of dry exfoliated graphite powder and 40 ℃ of dryings is directly tested.) with reference to accompanying drawing 2, as can see from Figure 2, (spectrogram a) locates still to remain with obvious graphite diffraction peak to exfoliated graphite in 2 θ=25.9 °, the phenomenon that moves to left has occurred in the position of diffraction peak, occur bimodal, mainly that crystalline structure changes because have new material to be inserted into the interlayer of graphite in graphite acidifying oxidation pretreatment process.Yet the graphite oxide (spectrogram b) through oxidation again locates to occur stronger graphene oxide diffraction peak in 2 θ=11 °, the completely dissolve of graphite diffraction peak, illustrate that graphite oxidation is more thorough, and the graphite oxide degree of oxidation obtained is high.
The FTIR of graphene oxide sample characterizes and (adopts the FTIR-8400s type Fourier transform infrared spectrometer of Japanese Shimadzu company to test sample, sweep limit: 4000～500cm
-1The sample preparation of KBr pressed disc method) with reference to accompanying drawing 3, result shows: the C-O stretching vibration in obvious epoxy group(ing) in spectrogram, occurs, the stretching vibration of C-OH, the flexural vibration of O-H and the stretching vibration peak of C=O, and intensity is larger, and the vibration of C=C weakens greatly, further illustrate the graphite oxide degree of oxidation higher.
The TEM of graphene oxide sample characterizes (adopting TECNAI G2F30 field transmission electron microscope) graphene oxide is dispersed in anhydrous ethanol solvent, and supersound process 20min takes a sample with disposable needle tubing, and drips on copper mesh and test.Photo is with reference to accompanying drawing 4, and as can be seen from Figure 4 the graphene oxide lamella is thinner, and the lamella area is large, presents fold stacking.
Embodiment 2
By 10g purity, be that 99% granularity is that the natural flake graphite of 180 μ m mixes with the 40mL concentrated nitric acid, from reactor bottom, add the hydrogen peroxide of 7mL, stirring reaction 30min, washing, obtain exfoliated graphite after drying; Take the 2g exfoliated graphite and mix with the vitriol oil of 100mL, slowly add 8g potassium permanganate, after mixing in ice-water bath ultrasonic assisted oxidation reaction 30min, ultrasonic power is 50kHz; Mixture is warming up to 60 ℃ and the lasting 12h of stirring, add the ultrasonic auxiliary lower stirring reaction 40min of deionized water, products therefrom first carries out eccentric cleaning with the mixing solutions of 10% dilute hydrochloric acid and 1% hydrogen peroxide 1:1, and then uses washed with de-ionized water, centrifugation, prepare graphene oxide.
The TEM of the graphene oxide sample obtained by the present embodiment characterize photo with reference to accompanying drawing 5(testing method with embodiment 1), as can be seen from Figure 5 the graphene oxide lamella is thinner, the synusia area is large, presents fold stacking.
Embodiment 3
By 10g purity, be that 90% granularity is that the natural flake graphite of 270 μ m mixes with the 50mL concentrated nitric acid, from reactor bottom, add the hydrogen peroxide of 10mL, stirring reaction 60min, washing, obtain exfoliated graphite after drying; Take the 2g exfoliated graphite and mix with the vitriol oil of 90mL, slowly add 8g potassium permanganate, after mixing in ice-water bath ultrasonic assisted oxidation reaction 30min, ultrasonic power is 40kHz; Mixture is warming up to 60 ℃ and the lasting 12h of stirring, add the ultrasonic auxiliary lower stirring reaction 30min of deionized water, products therefrom first carries out eccentric cleaning with the mixing solutions of 10% dilute hydrochloric acid and 1% hydrogen peroxide 1:1, and then uses washed with de-ionized water, centrifugation, prepare graphene oxide.
The TEM of the Graphene sample obtained by example characterize photo with reference to accompanying drawing 6(testing method with embodiment 1), as can be seen from the figure seldom, the graphene oxide lamella is thinner for the graphene sheet layer fold, the synusia area is large, presents fold stacking, edge occurs curling.
Embodiment 4
The preparation method is substantially with embodiment 1, and difference is that the purity of natural flake graphite used is 75%, and granularity is 200 μ m; Mixing acid with 100ml nitric acid and sulfuric acid during the preparation exfoliated graphite substitutes concentrated nitric acid, and wherein in mixing acid, nitric acid is 8:1 with the ratio of sulfuric acid.The graphene oxide obtained is characterized with TEM, and the graphene oxide lamella is thinner, and the synusia area is large, presents fold stacking, with the feature similarity of embodiment 1.
Embodiment 5
The preparation method is substantially with embodiment 1, difference is exfoliated graphite in ice-water bath during ultrasonic assisted oxidation, strong acid used is the concentrated nitric acid of volume ratio 3:1 and the mixing acid of the vitriol oil, strong oxidizer used is potassium bichromate, can obtain equally the degree of peeling off identical with embodiment 1 high, large stretch of graphene oxide that specific surface area is large.
Embodiment 6
The preparation method is substantially with embodiment 1, difference is exfoliated graphite in ice-water bath during ultrasonic assisted oxidation, strong acid used is perchloric acid, strong oxidizer used is that mass ratio is the SODIUMNITRATE of 1:1 and the mixture of potassium permanganate, can obtain equally the degree of peeling off identical with embodiment 1 high, large stretch of graphene oxide that specific surface area is large.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that those of ordinary skills make technical scheme of the present invention, all should fall in the definite protection domain of the claims in the present invention book.
Claims (10)
1. the preparation method of a large stretch of graphene oxide, is characterized in that, comprises the following steps:
(1) in reactor, natural flake graphite is mixed with the mixing acid of concentrated nitric acid or nitric acid and sulfuric acid composition, add hydrogen peroxide from reactor bottom, stirring reaction 10-60min, obtain exfoliated graphite after washing, drying;
(2) exfoliated graphite is mixed with strong acid, slowly adds strong oxidizer, after mixing in ice-water bath ultrasonic assisted oxidation reaction 30-60min;
(3) reaction mixture of step (2) is warming up to 50-60 ℃ and the lasting 6-12h of stirring, then add the ultrasonic auxiliary lower stirring reaction 10-30min of deionized water, products therefrom first cleans with the mixing solutions of dilute hydrochloric acid and hydrogen peroxide, and then use washed with de-ionized water, centrifugation, obtain graphene oxide.
2. method according to claim 1, it is characterized in that: the purity of described natural flake graphite is 75-99.9%, granularity is 150-270 μ m.
3. method according to claim 1, is characterized in that: natural flake graphite in described step (1): the mixing acid of concentrated nitric acid or nitric acid and sulfuric acid: hydrogen peroxide=1g:3-5mL:0.5-1mL.
4. method according to claim 1 is characterized in that: in described mixing acid, the volume ratio of nitric acid and sulfuric acid is (8-9): 1.
5. method according to claim 1, it is characterized in that: described nitric acid mass concentration is 85%, and h 2 so 4 concentration is 98%, and the hydrogen peroxide mass concentration is 60%.
6. method according to claim 1, it is characterized in that: in described step (2), ultrasonic assisted oxidation reaction strong acid used is the mixing acid that mix with arbitrary proportion the vitriol oil, concentrated nitric acid, perchloric acid or they, and strong oxidizer is the mixture that mix with arbitrary proportion potassium permanganate, SODIUMNITRATE, potassium bichromate, saltpetre or they.
7. method according to claim 1 is characterized in that: in described step (2), the ratio of exfoliated graphite and strong acid is 1g:25-50mL, and the part by weight of exfoliated graphite and strong oxidizer is 1:(3-5).
8. method according to claim 1 is characterized in that: in described step (2) and step (3), the ultrasonic power of ultrasonic assisted oxidation reaction is 40-50kHz.
9. method according to claim 1 is characterized in that: in described step (3), the mixing solutions of dilute hydrochloric acid and hydrogen peroxide is to be that 10% dilute hydrochloric acid and mass percent are that 1% hydrogen peroxide is mixed to get with volume ratio 1:1 by mass percent.
10. the graphene oxide that obtains of the described method of claim 1-9 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310317284.2A CN103408000B (en) | 2013-07-25 | 2013-07-25 | Preparation method for oxidized grapheme in large sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310317284.2A CN103408000B (en) | 2013-07-25 | 2013-07-25 | Preparation method for oxidized grapheme in large sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103408000A true CN103408000A (en) | 2013-11-27 |
| CN103408000B CN103408000B (en) | 2015-04-15 |
Family
ID=49601062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310317284.2A Active CN103408000B (en) | 2013-07-25 | 2013-07-25 | Preparation method for oxidized grapheme in large sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103408000B (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108711A (en) * | 2014-07-27 | 2014-10-22 | 北京化工大学 | Electrochemically assisted method for preparing monolayer large-size graphene oxide |
| CN104386680A (en) * | 2014-11-14 | 2015-03-04 | 沙嫣 | Method for large-scale preparation of bulky graphene |
| 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 |
| CN106115669A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene oxide |
| CN106235890A (en) * | 2016-09-23 | 2016-12-21 | 覃元子 | A kind of pot gallbladder with grapheme material and manufacture method thereof |
| EP3085664A4 (en) * | 2013-12-31 | 2017-03-15 | Shenzhen Cantonnet Energy Services Co. , Ltd. | Mixed-acid system-based method for preparation of graphene oxide and graphene |
| CZ307072B6 (en) * | 2016-11-24 | 2017-12-27 | Masarykova Univerzita | A method of preparing graphenoids and a graphhenoid obtainable by this method |
| CN107591538A (en) * | 2017-09-22 | 2018-01-16 | 圣盟（廊坊）新材料研究院有限公司 | A kind of preparation method of graphene-based anode material for lithium-ion batteries |
| CN108342811A (en) * | 2018-04-12 | 2018-07-31 | 中鸿纳米纤维技术丹阳有限公司 | A kind of environment-friendly type graphene nano textile fabric and preparation method thereof |
| CN108374207A (en) * | 2018-04-12 | 2018-08-07 | 中鸿纳米纤维技术丹阳有限公司 | A kind of processing method of graphene nano fiber cotton |
| CN108486686A (en) * | 2018-04-12 | 2018-09-04 | 中鸿纳米纤维技术丹阳有限公司 | A kind of preparation process of High-performance graphene Nanowire vinylon and cotton blend |
| CN108483434A (en) * | 2018-04-12 | 2018-09-04 | 中鸿纳米纤维技术丹阳有限公司 | A kind of preparation method of nanofiber production special graphite alkene stoste |
| CN110104639A (en) * | 2019-05-13 | 2019-08-09 | 四川欧迅能源工程科技有限公司 | A kind of extensive, controllable, inexpensive graphene preparation method |
| CN110453206A (en) * | 2019-08-08 | 2019-11-15 | 长春工业大学 | Press from both sides metal layer crystalline flake graphite and its preparation method and application |
| CN110980717A (en) * | 2019-10-29 | 2020-04-10 | 广东墨睿科技有限公司 | Method for preparing graphene oxide by using vermicular graphite |
| CN112010298A (en) * | 2020-08-14 | 2020-12-01 | 兰州大学 | Method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide |
| CN112374493A (en) * | 2020-12-28 | 2021-02-19 | 中国科学技术大学先进技术研究院 | Method for preparing monolayer graphene oxide with controllable sheet diameter size |
| CN113748085A (en) * | 2019-05-16 | 2021-12-03 | 安赛乐米塔尔公司 | Method for producing graphene oxide from expanded crystalline graphite |
| CN113860295A (en) * | 2021-10-20 | 2021-12-31 | 华南理工大学 | Method for preparing graphene oxide by using large-particle-size flake graphite |
| CN115050984A (en) * | 2022-06-15 | 2022-09-13 | 一汽解放汽车有限公司 | Preparation method and application of modified graphene oxide coating bipolar plate |
| CN115849359A (en) * | 2022-11-28 | 2023-03-28 | 内蒙古大学 | Preparation method of single-layer graphene oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| WO2011150325A2 (en) * | 2010-05-28 | 2011-12-01 | Board Of Regents, The University Of Texas System | Graphene oxide and graphite oxide catalysts and systems |
| CN102923696A (en) * | 2011-08-10 | 2013-02-13 | 中国科学院理化技术研究所 | Method for preparing graphene through photo-catalysis |
-
2013
- 2013-07-25 CN CN201310317284.2A patent/CN103408000B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011150325A2 (en) * | 2010-05-28 | 2011-12-01 | Board Of Regents, The University Of Texas System | Graphene oxide and graphite oxide catalysts and systems |
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| CN102923696A (en) * | 2011-08-10 | 2013-02-13 | 中国科学院理化技术研究所 | Method for preparing graphene through photo-catalysis |
Non-Patent Citations (4)
| Title |
|---|
| NINA I. KOVTYUKHOVA等: "Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations", 《CHEMISTRY OF MATERIALS》, vol. 11, 28 January 1999 (1999-01-28) * |
| 邹正光等: "超声辅助Hummers法制备氧化石墨烯", 《无机化学学报》, vol. 27, no. 9, 30 September 2011 (2011-09-30) * |
| 陈瑞灿等: "氧化还原法制备石墨烯及其表征", 《材料导报B：研究篇》, vol. 26, no. 6, 30 June 2012 (2012-06-30) * |
| 陈连清等: "单层边缘功能化石墨烯的制备和表征", 《中南民族大学学报 (自然科学版)》, vol. 30, no. 4, 31 December 2011 (2011-12-31) * |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3085664A4 (en) * | 2013-12-31 | 2017-03-15 | Shenzhen Cantonnet Energy Services Co. , Ltd. | Mixed-acid system-based method for preparation of graphene oxide and graphene |
| CN104108711A (en) * | 2014-07-27 | 2014-10-22 | 北京化工大学 | Electrochemically assisted method for preparing monolayer large-size graphene oxide |
| CN104108711B (en) * | 2014-07-27 | 2016-01-20 | 北京化工大学 | A kind of method adopting electrochemistry to assist to prepare individual layer large size graphene oxide |
| CN104386680A (en) * | 2014-11-14 | 2015-03-04 | 沙嫣 | Method for large-scale preparation of bulky graphene |
| CN104386680B (en) * | 2014-11-14 | 2016-05-11 | 上海史墨希新材料科技有限公司 | The method of large stretch of Graphene is prepared in scale |
| WO2016074393A1 (en) * | 2014-11-14 | 2016-05-19 | 上海史墨希新材料料技有限公司 | Method for large-scale preparation of bulky graphene |
| 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 |
| CN106115669A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene oxide |
| CN106235890A (en) * | 2016-09-23 | 2016-12-21 | 覃元子 | A kind of pot gallbladder with grapheme material and manufacture method thereof |
| CZ307072B6 (en) * | 2016-11-24 | 2017-12-27 | Masarykova Univerzita | A method of preparing graphenoids and a graphhenoid obtainable by this method |
| CN107591538A (en) * | 2017-09-22 | 2018-01-16 | 圣盟（廊坊）新材料研究院有限公司 | A kind of preparation method of graphene-based anode material for lithium-ion batteries |
| CN108374207A (en) * | 2018-04-12 | 2018-08-07 | 中鸿纳米纤维技术丹阳有限公司 | A kind of processing method of graphene nano fiber cotton |
| CN108342811A (en) * | 2018-04-12 | 2018-07-31 | 中鸿纳米纤维技术丹阳有限公司 | A kind of environment-friendly type graphene nano textile fabric and preparation method thereof |
| CN108486686A (en) * | 2018-04-12 | 2018-09-04 | 中鸿纳米纤维技术丹阳有限公司 | A kind of preparation process of High-performance graphene Nanowire vinylon and cotton blend |
| CN108483434A (en) * | 2018-04-12 | 2018-09-04 | 中鸿纳米纤维技术丹阳有限公司 | A kind of preparation method of nanofiber production special graphite alkene stoste |
| CN110104639A (en) * | 2019-05-13 | 2019-08-09 | 四川欧迅能源工程科技有限公司 | A kind of extensive, controllable, inexpensive graphene preparation method |
| CN113748085A (en) * | 2019-05-16 | 2021-12-03 | 安赛乐米塔尔公司 | Method for producing graphene oxide from expanded crystalline graphite |
| CN110453206B (en) * | 2019-08-08 | 2021-07-20 | 长春工业大学 | Metal-sandwiched layer flake graphite and preparation method and application thereof |
| CN110453206A (en) * | 2019-08-08 | 2019-11-15 | 长春工业大学 | Press from both sides metal layer crystalline flake graphite and its preparation method and application |
| CN110980717A (en) * | 2019-10-29 | 2020-04-10 | 广东墨睿科技有限公司 | Method for preparing graphene oxide by using vermicular graphite |
| CN112010298A (en) * | 2020-08-14 | 2020-12-01 | 兰州大学 | Method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide |
| CN112374493A (en) * | 2020-12-28 | 2021-02-19 | 中国科学技术大学先进技术研究院 | Method for preparing monolayer graphene oxide with controllable sheet diameter size |
| CN113860295A (en) * | 2021-10-20 | 2021-12-31 | 华南理工大学 | Method for preparing graphene oxide by using large-particle-size flake graphite |
| CN115050984A (en) * | 2022-06-15 | 2022-09-13 | 一汽解放汽车有限公司 | Preparation method and application of modified graphene oxide coating bipolar plate |
| CN115849359A (en) * | 2022-11-28 | 2023-03-28 | 内蒙古大学 | Preparation method of single-layer graphene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103408000B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103408000B (en) | Preparation method for oxidized grapheme in large sheet | |
| Dao et al. | Graphene prepared by thermal reduction–exfoliation of graphite oxide: Effect of raw graphite particle size on the properties of graphite oxide and graphene | |
| CN102694171B (en) | Hydrothermal preparation method for composite material of single-layer WS2 and graphene | |
| US8114375B2 (en) | Process for producing dispersible nano graphene platelets from oxidized graphite | |
| CN103408001B (en) | Micro-wave digestion prepares the method for bigger serface Graphene | |
| CN102464313B (en) | Preparation method of graphene | |
| CN102757038B (en) | Method for preparing graphene | |
| CN102153077A (en) | Method for preparing single-layer graphene with high carbon-oxygen ratio | |
| US8501318B2 (en) | Dispersible and conductive nano graphene platelets | |
| CN104386678B (en) | A kind of preparation method of Graphene | |
| CN102698774B (en) | Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material | |
| CN103950923A (en) | New method for preparing high-quality graphene | |
| CN102701192B (en) | Method for preparing monolayer MoS2 and graphene compounded nano material | |
| CN104071777B (en) | A kind of preparation method of Graphene | |
| CN104556017B (en) | A kind of magnanimity preparation method of high-quality graphene | |
| CN102757035B (en) | Preparation method of graphene | |
| CN102786045A (en) | Method for preparing oxidized graphene | |
| CN104108711B (en) | A kind of method adopting electrochemistry to assist to prepare individual layer large size graphene oxide | |
| CN102698666A (en) | Preparation method of graphene/nanometer particle composite materials based on infrared ray radiation | |
| CN103539106A (en) | Preparation method of carbon material | |
| CN109319771A (en) | A kind of preparation method of graphene | |
| CN103626163A (en) | Graphene preparation method | |
| KR20150119529A (en) | Method of manufacturing of large-area graphene oxide and the large-area graphene oxide thereby | |
| WO2015099378A1 (en) | Graphene production method, and graphene dispersion composition | |
| CN105789628B (en) | A kind of azepine graphene and manganese dioxide hybrid aerogel and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |