CN102730676B - Method for preparing graphene - Google Patents
Method for preparing graphene Download PDFInfo
- Publication number
- CN102730676B CN102730676B CN201210249137.1A CN201210249137A CN102730676B CN 102730676 B CN102730676 B CN 102730676B CN 201210249137 A CN201210249137 A CN 201210249137A CN 102730676 B CN102730676 B CN 102730676B
- Authority
- CN
- China
- Prior art keywords
- graphene
- ionic liquid
- conjunction
- preparation
- impurity
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method for preparing graphene, belonging to the technical field of materials. The method comprises the steps of: mixing natural flake graphite powder and ionic liquid; carrying out mechanical grinding under the anaerobic condition; then dispersing the obtained mixture in water; carrying out centrifugation to remove by-product; and volatilizing solvent (water) to obtain the graphene which is in an ionic liquid binding state. The method is low in raw material cost, simple in operation, high in efficiency, energy-saving and environment-friendly; and the graphene which is in the ionic liquid binding state and is prepared by the invention has the layer numbers within the range of 1-10, and does not contain oxidation group, so that excellent electric conduction and electrochemical catalytic activity are maintained, and the graphene is especially suitable for preparing a high-performance electrode.
Description
Technical field:
The present invention relates to material technology field, relate to particularly a kind of graphene preparation method, particularly a kind of ionic liquid is in conjunction with the preparation method of Graphene.
Background technology:
When the number of plies of graphite linings is less than 10 layers, be referred to as grapheme material, it shows more common three-dimensional graphite different structure and performance: theoretical specific surface area is up to 2600m
2/ g; There is outstanding heat conductivility (3000W/ (mK)) and mechanical property (1060 GPa); Electronic mobility (1 5000cm of high speed under room temperature
2/ (Vs)).Because of a series of specific physiques such as specific conductivity that have perfect quantum tunneling effect, half integral quantum hall effect, never disappear, grapheme material has obtained research widely and application the various fields such as preparing at matrix material, nano-device, electronic component, hydrogen storage material and sensor.
Up to the present, the known main method of preparing Graphene has several as follows:
(1) micromechanics stripping method [Novcselov K.S., et al.Science 306 (2004) 666].This method can only produce the very limited graphene film of quantity, and production efficiency is low, and productive rate is extremely restricted, only as fundamental research.
(2) epitaxial growth method [Berger C., et a1.Science 312 (2006) 1191; Pan Y., et a1.Adv.Mater 21 (2009) 2777].Although this expensive method can obtain high-quality Graphene, for the further investigation of Graphene basis problem and further provide a kind of novel method and ideal system in the application aspect device, but in epitaxial process, Graphene and matrix phase mutual effect cause the doping of electronics, can there is difference in the energy and the Fermi that cause dirac point, the graphene platelet of producing is often in uneven thickness, and the bonding characteristic that can affect carbon-coating between Graphene and matrix.
(3) oxidation reduction process [Tung V.C., et a1.Nature Nanotechn.4 (2009) 25; Sun Xuhui etc. a kind of method of preparing Graphene. patent of invention, application number 201210004009.0; Wu Li pearl etc. a kind of method of preparing Graphene. patent of invention, application number 201110093737.9].Oxidation reduction process refers to natural graphite and strong acid and strong oxidizing property substance reaction generation graphite oxide, through ultrasonic dispersion, be prepared into graphene oxide, add reductive agent to remove the oxy radical on graphene oxide surface, as carboxyl, epoxy group(ing) and hydroxyl, obtain Graphene.After oxidation reduction process is suggested, with its simple technique, becomes laboratory and prepare the easiest method of Graphene, obtain vast Graphene investigator's favor.Its shortcoming is that the Graphene of preparation exists certain defect, will cause finished-product material part electrical property loss of energy, and application is restricted.
(4) chemical Vapor deposition process (CVD) [Kim K.S., et a1.Nature457 (2009) 70; Ningguo's celebrating etc. the preparation method of a kind of Graphene, doped graphene or graphene complex. patent of invention, application number 201110306114.5].The sample that this method makes has guaranteed the perfect crystalline degree of Graphene sample, is expected to obtain the graphene film of high conductivity and strong mechanical performance.And can meet the requirement that high-quality graphene is prepared in mass-producing, but the electronic property of prepared Graphene is subject to the impact of substrate very large, cost is higher, complex process.
(5) solvent-thermal method [Wang H.L., e t a l.J.Am.Chem.Soc.131 (2009) 9910].Solvent-thermal method refers in special closed reactor and adopts organic solvent as reaction medium, by reaction system is heated to critical temperature, self produces high pressure and carry out method prepared by Graphene in reaction system.It has solved the problem that Graphene is prepared in mass-producing, and synthetic Graphene purity is higher, but the reaction times is relatively long, has also brought specific conductivity very low negative impact simultaneously.
(6) electrolytic process [Liu N., et al.J.Adv.Funct.Mater18 (2008) 1518; Zhou Mingjie etc. a kind of graphene preparation method. patent of invention, application number 201010538228.8].The inventive method is low for equipment requirements, and production technique is simple, workable, is suitable for suitability for industrialized production, can synthesize a large amount of Graphenes, but the surface of the Graphene synthesizing is all with a large amount of positive ions or negative ion or organism.
(7) solvent stripping method [Hamilton C.E., et a1.Nano Lett.9 (2009) 3460].Solvent stripping method is that a small amount of graphite is scattered in solvent, forms the dispersion liquid of lower concentration, utilizes hyperacoustic effect to destroy the Van der Waals force of graphite layers, and now solvent can insert graphite layers and peels off layer by layer, prepares Graphene.This method can not destroyed the structure of Graphene as oxidation reduction process, can prepare high-quality Graphene.For its application in fields such as microtronics, multifunctional composites provides wide application prospect, but the method productive rate is very low, limits its commercial applications.
Generally speaking, Graphene technology of preparing is desirable not enough at present.Therefore find a kind of laboratory that had both been applicable to study on a small scale, graphene preparation method that again can large-scale mass production is a problem in urgent need to solve.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of graphene preparation method, thereby to solve, current Graphene manufacturing cost is high, complicated operation, quality product is not high or productivity has lowly limited its problem for commercial applications.
The present invention mixes natural flake graphite powder with ionic liquid, then mechanical mill under oxygen free condition be scattered in gained mixture in water, centrifugal removal by product, and solvent flashing (water), obtains the Graphene of ionic liquid bonding state.The present invention specifically realizes by following steps:
A graphene preparation method, comprises the following steps:
(1), first by the natural flake graphite powder of certain mass ratio and ionic liquid mixed at room temperature;
Further, described ionic liquid is N-octyl group pyridine hexafluorophosphate, N-octyl group pyridinium tetrafluoroborate salt, N-octyl group pyridine nitrate, N-hexyl pyridine hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt or N-hexyl pyridine nitrate.
Further, the mass ratio of described natural flake graphite powder and ionic liquid is: 1:2-1:0.6.
(2), above-mentioned steps gained natural flake graphite powder-ionic liquid mixture is ground under oxygen free condition, obtain the mixture of graphene-containing;
Further, described oxygen free condition can adopt nitrogen or rare gas element deoxygenation.
Further, described abradant lapping apparatus material is agate, pottery, glass, stainless steel or tetrafluoroethylene; Rotor is smooth sphere or convex surface centrum; Grinding power is manpower or machinery; Grinding pressure is 1.5 * 10
5-8.0 * 10
5pascal, the time is 300-900 minute.
(3), the mixture of above-mentioned grinding gained graphene-containing is ionic liquid containing a small amount of impurity in conjunction with Graphene, this state can be applied (such as preparing electrode), also can be by the described ionic liquid containing a small amount of impurity ultrasonic being scattered in ultrapure water of mixture in conjunction with Graphene, obtain water system and mix suspension liquid;
Further, the described ionic liquid containing a small amount of impurity is not more than 3g/L in conjunction with the ultrasonic concentration being scattered in ultrapure water of mixture of Graphene, and ultrasonic power is 40-60 watt, and the time is 20 minutes.
(4), water system after above-mentioned ultrasonic dispersion is mixed to suspension liquid, and to pack centrifuge tube into centrifugal, collects upper strata ionic liquid and stablize suspension liquid in conjunction with Graphene, discards throw out;
Further, described centrifugal rotational speed is 1000-4000 rev/min.
(5), volatilization removes above-mentioned ionic liquid and stablizes the moisture in suspension liquid in conjunction with Graphene, obtains high-purity ionic liquid in conjunction with Graphene powder.
Further, described volatilization is removed above-mentioned ionic liquid and is stablized the moisture in suspension liquid in conjunction with Graphene, takes nature to dry or reduces pressure (vacuum) method solvent flashing.
The present invention also provides a kind of Graphene that utilizes aforesaid method to prepare.
The present invention also provides a kind of application that utilizes Graphene prepared by aforesaid method.
The present invention also provides a kind of electrochemical working electrode that utilizes Graphene prepared by aforesaid method to manufacture.
The present invention's beneficial effect compared with the conventional method:
1, raw materials cost is low.Natural flake graphite and ionic liquid are all large-scale commercial production commodity, cheap and easy to get.In addition without other any chemical reagent.
2, simple to operate, energy-efficient, production cost is low.Without valuable instrument and equipment, be both applicable to laboratory and studied on a small scale, again can large-scale mass production.Whole technical process takes less; Even if be not underhand polish, produce every kilogram of required energy source and power of Graphene be also not more than 12 kilowatts/time.
3, environmental friendliness.Manufacture process does not produce any waste with environmental hazard risk.
4, product is mainly the Graphene of ionic liquid bonding state, and its number of plies is between 1-10, and oxygen-freeization group, keeps fabulous conductivity and electrochemical catalysis activity, is particularly suitable for for preparing high-performance electrode.
Accompanying drawing explanation:
Fig. 1: Graphene preparation and applicating flow chart thereof.
Fig. 2: OPFP is in conjunction with the SEM photo (3D) of Graphene.
Fig. 3: the cyclic voltammogram on paste working electrode (b) prepared by the paste working electrode (a) that the 1.0mmol/L Tripotassium iron hexacyanide is prepared in conjunction with Graphene powder at OPFP and conventional graphite powder.
Fig. 4: [Bpy] BF
4sEM photo (3D) in conjunction with Graphene.
Fig. 5: 20 μ mol/L malachite greens are at [Bpy] BF
4cyclic voltammogram on paste working electrode (b) prepared by the paste working electrode (a) of preparing in conjunction with Graphene powder and conventional graphite powder.
Embodiment:
Below by embodiment, describe by reference to the accompanying drawings technical scheme of the present invention in detail, embodiment makes an explanation to technical scheme of the present invention, and protection scope of the present invention is not subject to the restriction of embodiment.
Embodiment 1
A kind of graphene preparation method, Fig. 1 is shown in by technical scheme schematic diagram, utilize natural flake graphite powder to mix with N-octyl group pyridine hexafluorophosphate (OPFP) ionic liquid, hand-ground under oxygen free condition, then gained mixture is scattered in water, centrifugal removal by product, solvent flashing (water), obtains the Graphene of ionic liquid bonding state.Concrete steps are as follows:
Step 1, by the natural flake graphite powder of mass ratio 1:0.6 and OPFP mixed at room temperature.
Step 2, mixture is placed in agate mortar, under nitrogen protection, hand lapping is 2 hours.
The ionic liquid that mixture after step 3, grinding is a small amount of impurity can directly be used for preparing or modification electrochemical working electrode in conjunction with Graphene, also can further process and obtain highly purified OPFP in conjunction with Graphene---be about to mixture 1g and move in 0.5L water, within under 40W power ultrasonic 20 minutes, disperse, obtain water system and mix suspension liquid.
Step 4, water system mixed to suspension liquid move into centrifuge tube, 2000 revs/min centrifugal 10 minutes, get upper strata ionic liquid and stablize suspension liquid in conjunction with Graphene, discard throw out.
Step 5, volatilization are removed above-mentioned ionic liquid and are stablized the moisture in suspension liquid in conjunction with Graphene, obtain high-purity ionic liquid in conjunction with Graphene powder, and OPFP is shown in Fig. 2 in conjunction with the SEM photo of Graphene.
Step 6, utilize highly purified OPFP to prepare high-performance electric chemistry working electrode or be used for modified electrode in conjunction with Graphene.Compare with the paste working electrode that tradition adopts Graphite Powder 99 to prepare, utilize the paste working electrode that highly purified OPFP is prepared in conjunction with Graphene powder to show significantly higher electron transfer rate and sensitivity (large current-responsive value) to the electric active molecule Tripotassium iron hexacyanide, its comparison diagram is shown in Fig. 3.
Embodiment 2
A graphene preparation method, Fig. 1 is shown in by technical scheme schematic diagram, utilizes natural flake graphite powder and N-hexyl pyridinium tetrafluoroborate salt ([Bpy] BF
4) ionic liquid mixes, mechanical mill under oxygen free condition, is then scattered in gained mixture in water, centrifugal removal by product, and solvent flashing (water), obtains the Graphene of ionic liquid bonding state.Concrete steps are as follows:
Step 1, by the natural flake graphite powder of mass ratio 1:2 and [Bpy] BF
4mixed at room temperature.
Step 2, mixture is placed in stainless cylinder of steel, under nitrogen protection, agitator drives diameter 3cm Stainless Steel Ball agitation grinding 5 hours.
The ionic liquid that mixture after step 3, grinding is a small amount of impurity can directly be used for preparing or modifying electrochemical working electrode in conjunction with Graphene, also can further process and obtain [Bpy] BF that purity is higher
4in conjunction with Graphene---be about to mixture 1g and move in 0.5L water, within 40W power ultrasonic 20 minutes, disperse, obtain water system and mix suspension liquid.
Step 4, water system mixed to suspension liquid move into centrifuge tube, 4000 revs/min centrifugal 5 minutes, get upper strata ionic liquid and stablize suspension liquid in conjunction with Graphene, discard throw out.
Step 5, volatilization are removed above-mentioned ionic liquid and are stablized the moisture in suspension liquid in conjunction with Graphene, obtain high purity [Bpy] BF
4ionic liquid is in conjunction with Graphene powder, [Bpy] BF
4fig. 4 is shown in by SEM photo in conjunction with Graphene.
Step 6, utilize highly purified [Bpy] BF
4in conjunction with Graphene, prepare high-performance electric chemistry working electrode or be used for modified electrode.Compare with the paste working electrode that tradition adopts Graphite Powder 99 to prepare, utilize highly purified [Bpy] BF
4the paste working electrode of preparing in conjunction with Graphene powder shows obvious electro catalytic activity (suboxide overpotential) and higher sensitivity (large current-responsive value) to malachite green, and its comparison diagram is shown in Fig. 5.
Embodiment 3
With N-octyl group pyridine nitrate, replace other step of N-octyl group pyridine hexafluorophosphate in embodiment 1 identical with embodiment 1, can prepare equally high-quality Graphene.
Embodiment 4
With N-hexyl pyridine hexafluorophosphate, replace other step of N-octyl group pyridine hexafluorophosphate in embodiment 1 identical with embodiment 1, can prepare equally high-quality Graphene.
Embodiment 5
With N-hexyl pyridinium tetrafluoroborate salt, replace other step of N-octyl group pyridine hexafluorophosphate in embodiment 1 identical with embodiment 1, can prepare equally high-quality Graphene.
Embodiment 6
With N-hexyl pyridine nitrate, replace other step of N-octyl group pyridine hexafluorophosphate in embodiment 1 identical with embodiment 1, can prepare equally high-quality Graphene.
Claims (9)
1. a graphene preparation method, is characterized in that comprising the following steps:
(1) first by the natural flake graphite powder of certain mass ratio and ionic liquid mixed at room temperature;
(2) above-mentioned steps gained natural flake graphite powder-ionic liquid mixture is ground under oxygen free condition, obtain the mixture of graphene-containing;
(3) mixture of above-mentioned grinding gained graphene-containing is ionic liquid containing a small amount of impurity in conjunction with Graphene;
Described a kind of graphene preparation method, is characterized in that described step (1) intermediate ion liquid is a kind of in N-octyl group pyridine hexafluorophosphate, N-octyl group pyridinium tetrafluoroborate salt, N-octyl group pyridine nitrate, N-hexyl pyridine hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt or the pure solution of N-hexyl pyridine nitrate.
2. a kind of graphene preparation method according to claim 1, is characterized in that the mass ratio of the middle natural flake graphite powder of described step (1) and ionic liquid is: 1:2-1:1.
3. a kind of graphene preparation method according to claim 1, is characterized in that in described step (2), oxygen free condition adopts nitrogen or rare gas element deoxygenation.
4. a kind of graphene preparation method according to claim 1, is characterized in that in described step (2), abradant lapping apparatus material is agate, pottery, glass, stainless steel or tetrafluoroethylene; Rotor is smooth sphere or convex surface centrum; Grinding power is manpower or machinery; Grinding pressure is 1.5 * 10
5-8.0 * 10
5pascal, the time is 300-900 minute.
5. a graphene preparation method, is characterized in that the ionic liquid containing a small amount of impurity of the step (3) described in the graphene preparation method described in any one claim 1 to 4 carries out steps of processing in conjunction with Graphene:
(1) the described ionic liquid containing a small amount of impurity is scattered in ultrapure water in conjunction with Graphene is ultrasonic, obtains water system and mix suspension liquid;
(2) above-mentioned water system after ultrasonic being mixed to suspension liquid, to pack centrifuge tube into centrifugal, collects upper strata ionic liquid and stablize suspension liquid in conjunction with Graphene, discards throw out;
(3) the above-mentioned ionic liquid of volatilization removal is stablized the moisture in suspension liquid in conjunction with Graphene, obtains high-purity ionic liquid in conjunction with Graphene.
6. a kind of graphene preparation method according to claim 5, it is characterized in that in described step (1) that the concentration that the ionic liquid containing a small amount of impurity is scattered in ultrapure water in conjunction with Graphene is not more than 3g/L, ultrasonic power is 40-60 watt, and the time is 20 minutes.
7. one kind is utilized the Graphene that prepared by method described in claim 6.
8. an application that utilizes the Graphene that prepared by method described in claim 6.
9. an electrochemical working electrode that utilizes the Graphene that prepared by method described in claim 6 to manufacture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210249137.1A CN102730676B (en) | 2012-07-18 | 2012-07-18 | Method for preparing graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210249137.1A CN102730676B (en) | 2012-07-18 | 2012-07-18 | Method for preparing graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102730676A CN102730676A (en) | 2012-10-17 |
| CN102730676B true CN102730676B (en) | 2014-03-26 |
Family
ID=46987082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210249137.1A Expired - Fee Related CN102730676B (en) | 2012-07-18 | 2012-07-18 | Method for preparing graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102730676B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016063036A1 (en) * | 2014-10-21 | 2016-04-28 | 2-Dtech Limited | Methods for the production of 2-d materials |
| RU2743523C1 (en) * | 2019-12-12 | 2021-02-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") | Method for producing graphene-containing suspensions and device for carrying out said method |
| RU2776502C1 (en) * | 2021-08-10 | 2022-07-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования «Тамбовский государственный технический университет» (ФГБОУ ВО «ТГТУ») | Device for the production of graphene-containing suspensions by cascading exfoliation of graphite |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787310A (en) * | 2012-10-31 | 2014-05-14 | 海洋王照明科技股份有限公司 | Boron-doped graphene composite thin film electrode material and preparation method thereof, and electrochemical capacitor and preparation method of electrochemical capacitor |
| CN103935982B (en) * | 2013-01-18 | 2016-01-13 | 海洋王照明科技股份有限公司 | The preparation method of graphene nanobelt |
| CN103971951B (en) * | 2013-01-28 | 2017-02-01 | 海洋王照明科技股份有限公司 | Preparing method for supercapacitor |
| CN103102514B (en) * | 2013-01-30 | 2015-01-21 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| CN103708442B (en) * | 2013-11-08 | 2015-10-07 | 江苏科技大学 | A kind of ionic liquid prepares the method for polymolecularity Graphene |
| CN103832963B (en) * | 2014-01-15 | 2015-12-09 | 华中科技大学 | A kind of preparation method of microbubble generator |
| CN103954673A (en) * | 2014-03-25 | 2014-07-30 | 西北师范大学 | Method for applying ionic liquid functionalized graphene modified electrode in detection of 5-hydroxytryptamine and dopamine |
| CN106829941A (en) * | 2017-04-07 | 2017-06-13 | 厦门大学 | A kind of preparation method of Graphene |
| CN110551556B (en) * | 2019-07-26 | 2021-06-04 | 西南交通大学 | Quaternary phosphonium salt-two-dimensional material composite lubricating additive, preparation method and use method thereof, and industrial lubricating oil |
| CN113387348B (en) * | 2020-08-14 | 2022-07-19 | 中国科学院过程工程研究所 | Method for preparing graphene by using composite ionic liquid |
| CN114426271A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214954A (en) * | 2008-01-22 | 2008-07-09 | 东北师范大学 | Method for preparing conductive single-layer graphite sheet modified by ionic liquid cation group |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
-
2012
- 2012-07-18 CN CN201210249137.1A patent/CN102730676B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214954A (en) * | 2008-01-22 | 2008-07-09 | 东北师范大学 | Method for preparing conductive single-layer graphite sheet modified by ionic liquid cation group |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
Non-Patent Citations (4)
| Title |
|---|
| Controllable selective exfoliation of high-quality graphene nanosheets and nanodots by ionic liquid assisted grinding;Nai Gui Shang et al.;《Chem. Commun.》;20120104;第48卷;1877-1879 * |
| Direct exfoliation of natural graphite into micrometre size few layers graphene sheets using ionic liquids;Xiqing Wang et al.;《Chem. Commun.》;20100519;第46卷;4487-4489 * |
| Nai Gui Shang et al..Controllable selective exfoliation of high-quality graphene nanosheets and nanodots by ionic liquid assisted grinding.《Chem. Commun.》.2012,第48卷1877-1879. |
| Xiqing Wang et al..Direct exfoliation of natural graphite into micrometre size few layers graphene sheets using ionic liquids.《Chem. Commun.》.2010,第46卷4487-4489. |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016063036A1 (en) * | 2014-10-21 | 2016-04-28 | 2-Dtech Limited | Methods for the production of 2-d materials |
| RU2743523C1 (en) * | 2019-12-12 | 2021-02-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") | Method for producing graphene-containing suspensions and device for carrying out said method |
| RU2776502C1 (en) * | 2021-08-10 | 2022-07-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования «Тамбовский государственный технический университет» (ФГБОУ ВО «ТГТУ») | Device for the production of graphene-containing suspensions by cascading exfoliation of graphite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102730676A (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102730676B (en) | Method for preparing graphene | |
| CN103950923B (en) | A kind of novel method preparing high-quality Graphene | |
| CN103337611B (en) | The preparation method of a kind of Graphene and composite titania material | |
| CN103466608B (en) | A kind of ball milling preparation method of Graphene | |
| CN102556941B (en) | A kind of cobaltosic oxide nano linear array, its preparation method and the purposes as lithium ion battery negative | |
| CN102757036B (en) | Preparation method of porous graphene | |
| CN102760866B (en) | Preparation method of nitrogen-doped graphene | |
| CN104386678B (en) | A kind of preparation method of Graphene | |
| CN103787328A (en) | Modified grapheme preparation method | |
| CN102698774B (en) | Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material | |
| CN103215469A (en) | Porous graphene, graphene/porous metal composite material, and preparation methods of porous graphene and composite material | |
| CN102001651B (en) | Method for preparing graphene based on hydroxylamine reduction | |
| CN102897751B (en) | A kind of method preparing graphene with high specific surface activity | |
| CN103451670B (en) | A kind of Electrochemical preparation method of Graphene | |
| CN103058176A (en) | Method for preparing graphene efficiently | |
| CN103570004A (en) | Simple large-scale preparation and functionalization method of graphene | |
| CN104817075A (en) | Preparation method of highly-dispersed graphene oxide nanobelt liquid | |
| CN102583338A (en) | High-quality graphene powder and preparation method thereof | |
| CN103420361A (en) | A method of preparing graphene by explosion | |
| Lee et al. | Electrochemical properties and characterization of various ZnO structures using a precipitation method | |
| CN103022468B (en) | Environment-friendly preparation method for high-specific-capacitance Mn3O4/graphene composite material for poles | |
| CN105789628B (en) | A kind of azepine graphene and manganese dioxide hybrid aerogel and its preparation method and application | |
| CN102701190A (en) | Process and method for preparing graphene in mixed solution of water and acetone | |
| CN102583271A (en) | Spine-like SbSe3 semiconductor hydrogen storage material and preparation method thereof | |
| CN106276885A (en) | The fast preparation method of high conductivity nitrogen-doped graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140326 Termination date: 20150718 |
|
| EXPY | Termination of patent right or utility model |