CN103408000B - Preparation method for oxidized grapheme in large sheet - Google Patents
Preparation method for oxidized grapheme in large sheet Download PDFInfo
- Publication number
- CN103408000B CN103408000B CN201310317284.2A CN201310317284A CN103408000B CN 103408000 B CN103408000 B CN 103408000B CN 201310317284 A CN201310317284 A CN 201310317284A CN 103408000 B CN103408000 B CN 103408000B
- Authority
- CN
- China
- Prior art keywords
- acid
- mixing
- graphite
- 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.)
- Active
Links
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 prepares Graphene by the method for mechanically peel graphite first, Graphene, as a kind of novel two-dimensional nano carbonaceous material, because it has unique stuctures and properties, enjoys the concern of people.A kind of cellular two-dirnentional structure material of hexagonal lattice be made up of with sp2 hybridized orbital carbon atom of Graphene, thickness in monolayer is 0.35nm, C-C bond distance is 0.142nm, is the elementary cell forming soccerballene, carbon nanotube and graphite, has the performances such as excellent conduction, heat conduction, mechanics and electrochemistry.Monoatomic layer grapheme material theoretical specific surface area is up to 2630m
2/ g, semiconductor 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 domestic and international Graphene has micromechanics stripping method, epitaxial growth method, chemical Vapor deposition process, oxidation reduction process, liquid phase stripping method etc.Oxidation reduction process is current comparatively common low cost, prepares the method for big area thin graphene material efficiently.High-purity natural graphite is oxidized by oxidation technology by the method, obtain basic molecular structure and be C hexagon and the graphene oxide of surface and a large amount of group such as hydroxyl, carboxyl, epoxy of marginal existence, graphene oxide is washed to neutrality, removed the oxy radical on its molecular structure again by the method for reduction, finally obtain the method for grapheme material.In the chemistry redox method preparation technology of Graphene, the technology of preparing of large stretch of thin-layer graphene oxide is particularly crucial.The method for oxidation of graphite mainly contains Brodie, Staudenmaier and Hummers tri-kinds of methods.Brodie method graphite and NaClO
4fully mix in beaker, in ice bath, add dense HNO
3, after mixing, mixture is heated to 60 DEG C, continues to stir 24h, then filter the oxidation graphite solid of gained, with the HCI solution cleaning of 5%, filter, then dry.The degree of oxidation of the graphite oxide obtained after washing is lower, and need carry out repeatedly oxide treatment to improve degree of oxidation, the reaction times is relatively long.The advantage of the method is that its degree of oxidation can utilize oxidization time to control, and the graphite oxide crystallinity of synthesis is high.But because adopting perchlorate to make oxygenant, danger is comparatively large, and can produce more toxic gas in reaction process.Staudenmaier method adopts vitriol oil system, and perchlorate and nitrosonitric acid are oxygenant, and the temperature of reaction system needs to maintain 0 DEG C always.Degree of oxidation increases with the increase in reaction times, controls 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, does not just occur graphite diffraction peak in the XRD figure of the product obtained after general oxidation 56h.In addition, the toxic gas substance C l produced in reaction process
2more.Hummers method adopts the vitriol oil and nitrate system, take permanganate as oxygenant, prepare graphite oxide through low temperature (less than 4 DEG C), middle temperature (about 35 DEG C) and high temperature (less than 98 DEG C) three step of reaction.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 occur swelling and leafing in water.At present, have with graphite microparticles or expanded graphite for raw material, adopt the patent report of Hummers legal system for graphene oxide of improvement, but with small grain size graphite microparticles for raw material time, its oxidation efficiency is higher, when taking flaky graphite as raw material, the peelable degree of its oxidation efficiency and graphite oxide is all poor; When taking expanded graphite as raw material, although the quasiflake graphite after expanding provides more contact area for strong acid and strong oxidizer, improve oxidation efficiency, but the huge expanding volume of expanded graphite makes oxidizing reaction need more acid, in addition, prepare in expanded graphite process at high temperature puffing, 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, first this preparation method carries out pre-treatment to graphite to prepare exfoliated graphite, then adopts ultrasonic wave added oxidizing reaction to prepare graphene oxide.The method is simple to operate, and oxidation efficiency is high, non-environmental-pollution, and the graphene oxide splitting 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, the mixing acid that natural flake graphite and concentrated nitric acid or nitric acid and sulfuric acid form is mixed, hydrogen peroxide is added (if added from top from reactor bottom, hydrogen peroxide easily decomposes, be unfavorable for the carrying out reacted), stirring reaction 10-60min, obtains exfoliated graphite after washing, drying;
(2) exfoliated graphite is mixed with strong acid, slowly adds strong oxidizer, after mixing in ice-water bath ultrasonic wave added oxidizing reaction 30-60min;
(3) reaction mixture of step (2) is warming up to 50-60 DEG C and Keep agitation 6-12h, add stirring reaction 10-30min under deionized water (ratio of preferred exfoliated graphite and deionized water is 1g:100mL) ultrasonic wave added, products therefrom first cleans with the mixing solutions of dilute hydrochloric acid and hydrogen peroxide, and then by washed with de-ionized water, centrifugation, obtains 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 preparing Graphene is high purity graphite, and the inventive method is not limited to 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 is to the purity of graphite and granularity not requirement, but from the angle reducing production cost of enhancing productivity, the purity of preferred graphite is 75-99.9%, and granularity is 150-270 μm.
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 preferably described concentration of nitric acid is 85%(mass percent), sulfuric acid concentration is 98%(mass percent), hydrogen peroxide concentration is 60%(mass percent).
Method of the present invention, the strong acid that wherein ultrasonic wave added oxidizing reaction is used in preferred described step (2) is the vitriol oil, concentrated nitric acid, perchloric acid or they are with the mixing acid of arbitrary proportion mixing, and strong oxidizer is potassium permanganate, SODIUMNITRATE, potassium bichromate, saltpetre or they are with the mixture of arbitrary proportion mixing.
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, required strong acid and the amount of strong oxidizer larger.
Method of the present invention, wherein the ultrasonic power of preferred described step (2) and the middle ultrasonic wave added oxidizing reaction of step (3) is 40-50kHz.
Method of the present invention, wherein in preferred described step (3) mixing solutions of dilute hydrochloric acid and hydrogen peroxide be by mass percent be 10% dilute hydrochloric acid and mass percent be 1% hydrogen peroxide be mixed to get with volume ratio 1:1.
The invention still further relates to the graphene oxide obtained by aforesaid method.
Difference from prior art is, the intercalation that first the present invention replaces solid oxidizing agent by hydrogen peroxide prepares exfoliated graphite, then adopts ultrasonic wave added oxidizing reaction to prepare graphene oxide.Greatly can not only improve the oxidation efficiency of graphite, and ultrasonic wave added reaction makes the graphite oxide of preparation without the need to peeling off, the Graphene splitting 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.
Below in conjunction with accompanying drawing, the preparation method to large stretch of graphene oxide of the present invention is described further.
Accompanying drawing explanation
Fig. 1 is that the SEM of the exfoliated graphite that example 1 of the present invention obtains characterizes photo;
Fig. 2 is that the XRD of the obtained exfoliated graphite of example of the present invention 1 and graphite oxide characterizes spectrogram;
Fig. 3 is that the FTIR of the graphite oxide that example 1 of the present invention obtains characterizes spectrogram;
Fig. 4 is that the TEM of the graphene oxide that example 1 of the present invention obtains characterizes photo;
Fig. 5 is that the TEM of the graphene oxide that example 2 of the present invention obtains characterizes photo;
Fig. 6 is that the TEM of the graphene oxide that example 3 of the present invention obtains characterizes photo.
Embodiment
Be below embodiment and testing data etc. thereof, but content of the present invention is not limited to the scope of these embodiments.
Embodiment 1
To be 99% granularity by 10g purity be, and the natural flake graphite of 150 μm mixes with 30mL concentrated nitric acid, and the concentration adding 5mL from reactor bottom is the hydrogen peroxide of 60%, stirring reaction 20min, and washing, obtains exfoliated graphite after drying; Take 2g exfoliated graphite to mix with the vitriol oil of 80mL, slowly add 6g potassium permanganate, after mixing in ice-water bath ultrasonic wave added oxidizing reaction 30min, ultrasonic power is 40kHz; Mixture is warming up to 50 DEG C and Keep agitation 10h, add stirring reaction 20min under 200mL deionized water ultrasonic wave added, products therefrom first uses 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 by washed with de-ionized water, centrifugation, obtains graphene oxide.
The SEM of the exfoliated graphite obtained by the present embodiment is characterized and (adopts MX2600FE scanning electronic microscope, Camscan company of Britain.The exfoliated graphite powder of drying 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, part graphite flake layer is stripped 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 XRD sign to material.X-ray source is Cu – K alpha-ray (λ=0.15406nm), voltage 40kV, electric current 40mA, and sweep limit 2 θ is between 5 ° ~ 70 °, sweep velocity 6 °/min, scanning step 0.02 °, and detector is scintillometer.The exfoliated graphite powder of drying and 40 DEG C of dry graphene oxide samples are directly tested.) with reference to accompanying drawing 2, as can see from Figure 2, (a) in 2 θ=25.9, a ° place still remains with obvious graphite diffraction peak to spectrogram to exfoliated graphite, the position of diffraction peak there occurs the phenomenon that moves to left, occur bimodal, mainly because have new material to be inserted into the interlayer of graphite in graphite acidifying oxidation pretreatment process, crystalline structure changes.But the graphite oxide (spectrogram b) through being again oxidized is in 2 θ=11, and the completely dissolve of graphite diffraction peak appears stronger graphene oxide diffraction peak, in a ° place, illustrate that graphite oxidation is relatively more thorough, 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 Corporation to test sample, sweep limit: 4000 ~ 500cm
-1; The sample preparation of KBr pressed disc method) with reference to accompanying drawing 3, result shows: occur the C-O stretching vibration in obvious epoxy group(ing) in spectrogram, 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 graphite oxide degree of oxidation higher.
The TEM of graphene oxide sample characterizes, and graphene oxide is dispersed in anhydrous ethanol solvent by (adopting TECNAI G2F30 Flied emission transmission electron microscope), and supersound process 20min, samples 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 graphene oxide lamella is thinner, and lamella area is large, presents fold stacking.
Embodiment 2
To be 99% granularity by 10g purity be, and the natural flake graphite of 180 μm mixes with 40mL concentrated nitric acid, and add the hydrogen peroxide of 7mL from reactor bottom, stirring reaction 30min, washing, obtains exfoliated graphite after drying; Take 2g exfoliated graphite to mix with the vitriol oil of 100mL, slowly add 8g potassium permanganate, after mixing in ice-water bath ultrasonic wave added oxidizing reaction 30min, ultrasonic power is 50kHz; Mixture is warming up to 60 DEG C and Keep agitation 12h, add stirring reaction 40min under deionized water ultrasonic wave added, products therefrom first carries out eccentric cleaning with the mixing solutions of 10% dilute hydrochloric acid and 1% hydrogen peroxide 1:1, and then by washed with de-ionized water, centrifugation, prepares graphene oxide.
The TEM of the graphene oxide sample obtained by the present embodiment characterizes photo with reference to accompanying drawing 5(testing method with embodiment 1), as can be seen from Figure 5 graphene oxide lamella is thinner, and synusia area is large, presents fold stacking.
Embodiment 3
To be 90% granularity by 10g purity be, and the natural flake graphite of 270 μm mixes with 50mL concentrated nitric acid, and add the hydrogen peroxide of 10mL from reactor bottom, stirring reaction 60min, washing, obtains exfoliated graphite after drying; Take 2g exfoliated graphite to mix with the vitriol oil of 90mL, slowly add 8g potassium permanganate, after mixing in ice-water bath ultrasonic wave added oxidizing reaction 30min, ultrasonic power is 40kHz; Mixture is warming up to 60 DEG C and Keep agitation 12h, add stirring reaction 30min under deionized water ultrasonic wave added, products therefrom first carries out eccentric cleaning with the mixing solutions of 10% dilute hydrochloric acid and 1% hydrogen peroxide 1:1, and then by washed with de-ionized water, centrifugation, prepares graphene oxide.
The TEM of the Graphene sample obtained by example characterizes photo with reference to accompanying drawing 6(testing method with embodiment 1), as can be seen from the figure graphene sheet layer fold is little, and graphene oxide lamella is thinner, and synusia area is large, presents fold stacking, and edge occurs curling.
Embodiment 4
Preparation method is substantially with embodiment 1, and difference is that the purity of natural flake graphite used is 75%, and granularity is 200 μm; Substitute concentrated nitric acid with the mixing acid of 100ml nitric acid and sulfuric acid during preparation exfoliated graphite, wherein in mixing acid, the ratio of nitric acid and sulfuric acid is 8:1.Characterized by the graphene oxide TEM obtained, graphene oxide lamella is thinner, and synusia area is large, presents fold stacking, with the feature similarity of embodiment 1.
Embodiment 5
Preparation method is substantially with embodiment 1, when difference is that ultrasonic wave added is oxidized in ice-water bath by exfoliated graphite, 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, same to obtain the splitting identical with embodiment 1 high, large stretch of graphene oxide that specific surface area is large.
Embodiment 6
Preparation method is substantially with embodiment 1, when difference is that ultrasonic wave added is oxidized in ice-water bath by exfoliated graphite, strong acid used is perchloric acid, strong oxidizer used is mass ratio is the SODIUMNITRATE of 1:1 and the mixture of potassium permanganate, same to obtain the splitting identical with embodiment 1 high, large stretch of graphene oxide that specific surface area is large.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (3)
1. a preparation method for large stretch of graphene oxide, is characterized in that, comprises the following steps:
(1) in reactor, the mixing acid that natural flake graphite and concentrated nitric acid or nitric acid and sulfuric acid form is mixed, add hydrogen peroxide from reactor bottom, stirring reaction 10-60min, after washing, drying, obtain exfoliated graphite;
(2) exfoliated graphite is mixed with strong acid, slowly adds strong oxidizer, after mixing in ice-water bath ultrasonic wave added oxidizing reaction 30-60min;
(3) reaction mixture of step (2) is warming up to 50-60 DEG C and Keep agitation 6-12h, then stirring reaction 10-30min under deionized water ultrasonic wave added is added, products therefrom first cleans with the mixing solutions of dilute hydrochloric acid and hydrogen peroxide, and then by washed with de-ionized water, centrifugation, obtains graphene oxide;
The purity of described natural flake graphite is 75% or 90%, and granularity is 150-270 μm;
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;
Described nitric acid mass concentration is 85%, and h 2 so 4 concentration is 98%, and hydrogen peroxide mass concentration is 60%;
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);
The ultrasonic power of described step (2) and the middle ultrasonic wave added oxidizing reaction of step (3) is 40-50kHz;
In described step (3) mixing solutions of dilute hydrochloric acid and hydrogen peroxide be by mass percent be 10% dilute hydrochloric acid and mass percent be 1% hydrogen peroxide be mixed to get with volume ratio 1:1.
2. 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.
3. method according to claim 1, it is characterized in that: the strong acid that ultrasonic wave added oxidizing reaction is used in described step (2) is the vitriol oil, concentrated nitric acid, perchloric acid or they are with the mixing acid of arbitrary proportion mixing, strong oxidizer is potassium permanganate, SODIUMNITRATE, potassium bichromate, saltpetre or they are with the mixture of arbitrary proportion mixing.
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 CN103408000A (en) | 2013-11-27 |
| CN103408000B true 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) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9550679B2 (en) * | 2013-12-31 | 2017-01-24 | Shenzhen Cantonnet Energy Services Co., Ltd. | Preparation method of graphene and graphene oxide based on mixed acid system |
| 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 |
| 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 |
| CN105692599B (en) * | 2016-01-25 | 2017-08-25 | 浙江碳谷上希材料科技有限公司 | A kind of preparation method without fragment super large piece graphene oxide |
| CN106115669B (en) * | 2016-06-20 | 2019-02-12 | 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 |
| CZ2016732A3 (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 |
| 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 |
| 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 |
| 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 |
| 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 |
| WO2020229881A1 (en) * | 2019-05-16 | 2020-11-19 | Arcelormittal | A method for the manufacture of graphene oxide from expanded kish 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 |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011150329A2 (en) * | 2010-05-28 | 2011-12-01 | Board Of Regents, The University Of Texas System | Carbocatalysts for chemical transformations |
| CN102153075B (en) * | 2011-03-22 | 2013-06-19 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| CN102923696B (en) * | 2011-08-10 | 2016-03-09 | 中国科学院理化技术研究所 | The method of Graphene is prepared in a kind of photochemical catalysis |
-
2013
- 2013-07-25 CN CN201310317284.2A patent/CN103408000B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103408000A (en) | 2013-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103408000B (en) | Preparation method for oxidized grapheme in large sheet | |
| CN103408001B (en) | Micro-wave digestion prepares the method for bigger serface Graphene | |
| CN102694171B (en) | Hydrothermal preparation method for composite material of single-layer WS2 and graphene | |
| CN102153077A (en) | Method for preparing single-layer graphene with high carbon-oxygen ratio | |
| CN101591014B (en) | Method for realizing large-scale preparation of monolayer oxidized graphene | |
| CN102464313B (en) | Preparation method of graphene | |
| CN102225754B (en) | Preparation method of graphene oxide and preparation method of graphene | |
| CN102698774B (en) | Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material | |
| CN102757038A (en) | Method for preparing graphene | |
| CN103950923A (en) | New method for preparing high-quality graphene | |
| CN104163421B (en) | The preparation method of the cotton-shaped graphene-based bottom material of a kind of three-dimensional and application thereof | |
| CN102701192B (en) | Method for preparing monolayer MoS2 and graphene compounded nano material | |
| CN102698666B (en) | Based on the preparation method of the graphene/nanometer particle composite material of infrared irridiation | |
| CN104071777B (en) | A kind of preparation method of Graphene | |
| CN102786045A (en) | Method for preparing oxidized graphene | |
| CN104556017B (en) | A kind of magnanimity preparation method of high-quality graphene | |
| CN104386678A (en) | Preparation method of graphene | |
| CN102757035B (en) | Preparation method of graphene | |
| CN104108711B (en) | A kind of method adopting electrochemistry to assist to prepare individual layer large size graphene oxide | |
| CN102709559B (en) | MoS2 nanobelt and graphene composite nanometer material and preparation method of composite nanometer material | |
| CN105789628B (en) | A kind of azepine graphene and manganese dioxide hybrid aerogel and its preparation method and application | |
| CN108622887B (en) | Method for preparing graphene through microwave puffing | |
| WO2015099378A1 (en) | Graphene production method, and graphene dispersion composition | |
| CN102951632A (en) | Preparation method of single-layer graphene oxide solution | |
| CN109301231B (en) | MoO (MoO)3Composite carbon dot lithium ion battery anode material and preparation method thereof |
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 |