CN104495810A - Environmental-friendly method for large-scale preparation of graphene - Google Patents
Environmental-friendly method for large-scale preparation of graphene Download PDFInfo
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Abstract
The invention provides an environmental-friendly method for large-scale preparation of graphene. A water-soluble organic matter melt is used for assisting in three-roller stripping to prepare the grapheme. The environmental-friendly method specifically comprises the following steps: (1) weighing a water-soluble organic matter and graphite in the mass ratio of (5: 1)-(500:1); (2) putting the water-soluble organic matter on rollers of a three-roller grinding machine, heating the rollers till a softening point of the water-soluble organic matter is reached to prepare an adhesive, operating the three-roller grinding machine, spreading the adhesive on the rollers of the three-roller grinding machine, further slowly adding the graphite, and performing grinding and stripping on the added graphite; and (3) immersing a product obtained in the step (2) into distilled water and washing to remove the water-soluble organic matter so as to obtain the graphene. According to the green method provided by the invention, a physical method is adopted for preparing the graphene, and the preparation process is environmental friendly, non-toxic and harmless, and can be applied to first-layer safety in the biomedical field; and furthermore, the method has the advantages of no special requirements on equipment, low cost, high efficiency, large-scale production and the like, and is simple and easy to operate.
Description
Technical field
The present invention relates to technical field of graphene, particularly relate to a kind of green method preparing Graphene on a large scale.
Background technology
Graphene is as a kind of novel Two-dimensional Carbon material, there is unique constitutional features and excellent electricity, mechanics, optics and thermal property, be with a wide range of applications in fields such as nano electron device, energy storage material, catalysis, sensor, pharmaceutical carrier and functional materials.Research shows, Graphene is at biomedical sector, and comprising the aspects such as targeted drug conveying, cell imaging, biological detection, oncotherapy has huge application prospect.But Graphene also needs to consider biological effect and security in the application of biomedical sector.If preparation technology's environmental protection, nontoxic, it has just been guaranteed in the first layer security of the application of biomedical sector, only need consider Graphene and living things system interaction mechanism.
Current, the preparation method of Graphene mainly contains chemical reduction graphene oxide method, the chemical vapor precipitator method, crystal epitaxy method, mechanically peel method etc.Wherein chemical reduction graphene oxide method is fully peeled off in water by graphite oxide, then carry out chemical reduction to it or thermal reduction obtains Graphene, and the method is considered to one and most possibly realizes Graphene industrialization and be prepared into important method.But due to the process through Strong oxdiative-reduction, the electron conjugated structure of graphene sheet layer is damaged, and reduces its physical and chemical performance.And need pyroprocessing in the oxidising process of graphite, or use the chemical substance that hydrazine hydrate, sodium borohydride etc. are poisonous, not only power consumption is large, efficiency is low, cost is high, and contaminate environment.
Catalytic growth after the chemical vapor precipitator method mainly utilize gaseous carbon source at high temperature to decompose on matrix surface prepares Graphene, and the method prepares the important method of high quality and big area single-layer graphene.But its working condition is comparatively harsh, power consumption is large, and cost is high.
Silicon carbide epitaxial growth method is by heating monocrystalline silicon carbide, under the high temperature conditions, is etched away by the Si on surface, and carbon atom is separated out and reconfigures formation Graphene, the Graphene quality comparation that the method is prepared is high.But its Graphene obtained is the mixture of individual layer and multilayer mostly, and there is stronger effect with matrix and not easily shift, making the method not easily large-scale production.
Mechanically peel method is by the limellar stripping of certain mechanical force by Graphene, thus the Graphene that preparation defect is less.The mechanically peel method of current appearance mainly contains following 4 kinds:
(1) " tear tape " method: highly oriented pyrolytic graphite is constantly peeled off repeatedly by adhesive tape by Geim study group, then transfers on silicon chip by the sample obtained, and finally falls adhesive tape with acetone solution, is prepared into single-layer graphene first.But the method productive rate is low, be difficult to realize extensive preparation.
(2) liquid phase stripping method: namely directly by ultrasonic or ball milling, graphite flake layer is peeled off under liquid-phase system.Coleman study group is in METHYLPYRROLIDONE solvent or carry out ultrasonic for a long time in the aqueous solution adding tensio-active agent to graphite, prepares individual layer and minority layer graphene.Chen Guohua study group utilizes wet ball grinding to be carry out ball milling to Graphite Powder 99 in the organic solvent of 30 – 45mNm-1 to prepare Graphene in surface tension.But the solvent used in ultrasonic and ball milling method and tensio-active agent are difficult to thorough removing, not only affect the practical application of Graphene, and the cost of removing organic solvent and tensio-active agent is high.
(3) three roller methods: Chen Guohua study group utilizes industrial common complete processing three roller stripping method, macromolecule dissolution is obtained sizing agent in organic solvent, by three-roller tool power and grinding distribution effect thereof, use for reference the original preparation method " adhesive tape method " of Graphene, graphite is peeled off obtained Graphene layer by layer.Concrete operations are for be dissolved in o-phthalic acid dibutyl ester by PVC, obtained sizing agent after magnetic force constant temperature 250 DEG C of heated and stirred 30min, macromolecular adhesive and graphite flake are added from the opening for feed of three-roller tool successively, not stall along with three rollers is moved, by continuous exfoliated graphite, be finally prepared into that defect is few, the Graphene of individual layer and minority layer.But because the Graphene obtained needs to utilize a large amount of organic solvent such as acetone, tetrahydrofuran (THF), pimelinketone etc. or heat to remove macromolecular adhesive, the high and contaminate environment of cost, limits it in industrialization large-scale production and application.
(4) solid particulate auxiliary machinery stripping method: Wang Lidong, Fei Weidong [Wang Lidong, Fei Weidong, high-efficiency and low-cost mechanical stripping prepares the method [P] of Graphene or graphene oxide, Chinese patent: CN101817516A, 2010-09-01] invent the method that high-efficiency and low-cost mechanical stripping prepares Graphene or graphene oxide, the bright use automation of the party, by solid particulate up-stripping process small in a large number, by solid particulate to the shearing of carbon materials and effect of impact, increase the contact area in stripping process and peel off number of times.But preparation method's work system that this invention provides is complicated, can with an organic solvent etc., contaminate environment, limits its scale operation industrially.
Therefore, a kind of simple in the urgent need to developing, cost is low, productive rate is high, pollution-free, the environmental protection novel preparation method easily promoted the use of.
Summary of the invention
The object of the invention is to solve the high cost, poor efficiency, the contaminate environment that exist in existing graphene preparation technology, can not industrial scale produce problem, provide a kind of green method preparing Graphene on a large scale.
To achieve these goals, the present invention adopts following technical scheme:
Prepare the green method of Graphene on a large scale, comprise the following steps:
(1) be 5:1 ~ 500:1 according to the mass ratio of water soluble organic substance and graphite, take water soluble organic substance and graphite is for subsequent use; This water soluble organic substance, for reaching its softening temperature when temperature, namely obtains the water soluble organic substance melt with gumminess;
(2) water soluble organic substance is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of water soluble organic substance to be achieved, the obtained water soluble organic substance melt as sizing agent, bring into operation three-roll grinder, treats that water soluble organic substance melt is laid on the roller of three-roll grinder, more slowly add graphite, three-roll grinder continues operation and carries out grinding stripping to the graphite added, and obtains Graphene and water soluble organic substance melted blend;
(3) Graphene step (2) obtained and water soluble organic substance melted blend are immersed in distilled water, wash 3-5 time, to remove water soluble organic substance, namely obtain Graphene.
Described water soluble organic substance adopts one or more the mixture in water-soluble monose, disaccharides, oligose, any two kinds and above mixing time be any proportioning.
Described water-soluble monose adopts glucose, fructose, semi-lactosi, sorbose, tagatose, inositol or seminose; Described water-soluble disaccharides adopts sucrose, lactose or maltose; Described water soluble oligosaccharide adopts raffinose, wood sugar, trehalose, stachyose, cyclodextrine, malto-oligosaccharide, fructose oligosaccharides or soybean oligosaccharide.
Described graphite is one or more the mixture in natural graphite, expanded graphite, high orientation graphite and thermo-cracking graphite, any two kinds and above mixing time be any proportioning.
In described step (2), the time that three-roll grinder peels off graphite is 0.5 ~ 72h.
Compared with prior art, advantage of the present invention is:
(1) the present invention utilizes water soluble organic substance melt to assist three-roll grinder to peel off graphite, obtains Graphene and water soluble organic substance melted blend, then removes water soluble organic substance melt with distilled water wash, thus obtain Graphene.The present invention is using water soluble organic substance melt as sizing agent, " tear tape " method of imitation prepares Graphene, what improve Chen Guohua study group is dissolved in o-phthalic acid dibutyl ester by PVC, obtained sizing agent after magnetic force constant temperature 250 DEG C of heated and stirred 30min, then macromolecular adhesive and graphite flake are added from the opening for feed of three-roller tool successively, utilize three rollers to peel off graphite, finally use organic solvent such as acetone or heat to remove the preparation method of macromolecular adhesive.There is cost low, and environmental protection, can industrialization scale operation be carried out.And whole preparation technology's environmental protection, nontoxic, determine its first layer security in biomedical applications field.
(2) Wang Lidong, the high-efficiency and low-cost mechanical stripping of Fei Weidong invention prepares the method [Wang Lidong of Graphene or graphene oxide, Fei Weidong, high-efficiency and low-cost mechanical stripping prepares the method [P] of Graphene or graphene oxide, Chinese patent: CN101817516A, 2010-09-01], the bright use automation of the party, by solid particulate up-stripping process small in a large number, by solid particulate to the shearing of carbon materials and effect of impact, increase the contact area in stripping process and peel off number of times, relative to this invention, principle of the present invention utilizes using water soluble organic substance melt as sizing agent, use for reference " adhesive tape method " and prepare Graphene, but not carry out mechanically peel using a large amount of minute solid particles as auxiliary.Have simple for process, there is environment friendly, easily promote the use of, be applicable to industrial scale and produce.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to following embodiment.
Embodiment 1:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take expanded graphite 4g, glucose 20g, the mass ratio of glucose and expanded graphite is 5:1;
(2) glucose is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of glucose to be achieved 130 DEG C, the obtained glucose melt as sizing agent, bring into operation three-roll grinder, treats that glucose melt is laid on the roller of three-roll grinder, more slowly add expanded graphite, three-roll grinder continues operation and carries out grinding stripping 30min to the expanded graphite added, and obtains Graphene and glucose melted blend;
(3) Graphene step (2) obtained and glucose melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent glucose melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 2:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take natural graphite 4g, maltose 200g, the mass ratio of maltose and natural graphite is 50:1;
(2) maltose is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of maltose to be achieved 95 DEG C, the obtained maltose melt as sizing agent, bring into operation three-roll grinder, treats that maltose melt is laid on the roller of three-roll grinder, more slowly add natural graphite, three-roll grinder continues operation and carries out grinding stripping 2h to the natural graphite added, and obtains Graphene and maltose melted blend;
(3) Graphene step (2) obtained and maltose melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent maltose melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 3:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take thermo-cracking graphite 2g, raffinose 500g, the mass ratio of raffinose and thermo-cracking graphite is 250:1;
(2) raffinose is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of raffinose to be achieved 65 DEG C, the obtained raffinose melt as sizing agent, bring into operation three-roll grinder, treats that raffinose melt is laid on the roller of three-roll grinder, more slowly add thermo-cracking graphite, three-roll grinder continues operation and carries out grinding stripping 24h to the thermo-cracking graphite added, and obtains Graphene and raffinose melted blend;
(3) Graphene step (2) obtained and raffinose melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent raffinose melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 4:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take high orientation graphite 3g, sucrose 90g, the mass ratio of sucrose and high orientation graphite is 30:1;
(2) sucrose is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of sucrose to be achieved 165 DEG C, the obtained sucrose melt as sizing agent, bring into operation three-roll grinder, treats that sucrose melt is laid on the roller of three-roll grinder, more slowly add high orientation graphite, three-roll grinder continues operation and carries out grinding stripping 48h to the high orientation graphite added, and obtains Graphene and sucrose melted blend;
(3) Graphene step (2) obtained and sucrose melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent sucrose melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 5:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take expanded graphite 2g, natural graphite 1g, wood sugar 1200g, the mass ratio of wood sugar and graphite is 400:1;
(2) wood sugar is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of wood sugar to be achieved 75 DEG C, the obtained wood sugar melt as sizing agent, bring into operation three-roll grinder, treats that wood sugar melt is laid on the roller of three-roll grinder, more slowly add expanded graphite and natural graphite, three-roll grinder continues operation and carries out grinding stripping 60h to the expanded graphite added and natural graphite, obtains Graphene and wood sugar melted blend;
(3) Graphene step (2) obtained and wood sugar melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent wood sugar melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 6:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take thermo-cracking graphite 2g, fructose 1000g, the mass ratio of fructose and thermo-cracking graphite is 500:1;
(2) fructose is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of fructose to be achieved 80 DEG C, the obtained fructose melt as sizing agent, bring into operation three-roll grinder, treats that fructose melt is laid on the roller of three-roll grinder, more slowly add thermo-cracking graphite, three-roll grinder continues operation and carries out grinding stripping 72h to the thermo-cracking graphite added, and obtains Graphene and fructose melted blend;
(3) Graphene step (2) obtained and fructose melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent fructose melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 7:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take expanded graphite 2g, semi-lactosi 400g, the mass ratio of semi-lactosi and expanded graphite is 200:1;
(2) semi-lactosi is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of semi-lactosi to be achieved 140 DEG C, the obtained semi-lactosi melt as sizing agent, bring into operation three-roll grinder, treats that semi-lactosi melt is laid on the roller of three-roll grinder, more slowly add expanded graphite, three-roll grinder continues operation and carries out grinding stripping 8h to the expanded graphite added, and obtains Graphene and semi-lactosi melted blend;
(3) Graphene step (2) obtained and semi-lactosi melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent semi-lactosi melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 8:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take expanded graphite 4g, glucose 25g, maltose 25g, sucrose 30g, the mass ratio of organism and graphite is 20:1;
(2) glucose, maltose and sucrose are positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of sucrose to be achieved 165 DEG C, obtained as sizing agent by the mixing organism melt of glucose melt, maltose melt and sucrose melt-mixing, bring into operation three-roll grinder, treat that this mixing organism melt is laid on the roller of three-roll grinder, slowly add expanded graphite again, three-roll grinder continues operation and carries out grinding stripping 30h to the expanded graphite added, and obtains Graphene and mixing organism melted blend;
(3) Graphene step (2) obtained and mixing organism melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent mixing organism melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
Embodiment 9:
Prepare the green method of Graphene on a large scale, comprise the steps:
(1) take expanded graphite 2.5g, thermo-cracking graphite 2.5g, sucrose 25g, fructose 25g, the mass ratio of organism and graphite is 10:1;
(2) sucrose and fructose are positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of sucrose to be achieved 165 DEG C, obtained as sizing agent by the mixing organism melt of sucrose melt and fructose melt-mixing, bring into operation three-roll grinder, treat that this mixing organism melt is laid on the roller of three-roll grinder, slowly add expanded graphite and thermo-cracking graphite again, three-roll grinder continues operation and carries out grinding stripping 4h to the expanded graphite added and thermo-cracking graphite, obtains Graphene and mixing organism melted blend;
(3) Graphene step (2) obtained and mixing organism melted blend are immersed in distilled water, after first using 100 DEG C of distilled water washs 3 times, again with normal-temperature distilled water washing 2 times, removing sizing agent mixing organism melt, vacuum filtration, finally by the 100 DEG C of dry 12h in electric drying oven with forced convection of the product after suction filtration, obtain Graphene.
In the present invention, water soluble organic substance is heated into water soluble organic substance melt to realize in the following way: the gap in the usual way before, during and after adjustment three-roll grinder between roller, again part aqueous organism is positioned over respectively on three rollers, heating roller makes water soluble organic substance be melted into have the melt of gumminess, being poured on by remaining water soluble organic substance has on the melt of gumminess again, water soluble organic substance has been stuck, can not drop to outside roller, continue heating and make whole water soluble organic substances all be melted into the melt with gumminess.
Claims (5)
1. prepare the green method of Graphene on a large scale, it is characterized in that, comprise the following steps:
(1) be 5:1 ~ 500:1 according to the mass ratio of water soluble organic substance and graphite, take water soluble organic substance and graphite is for subsequent use; This water soluble organic substance reaches its softening temperature when temperature, namely obtains the water soluble organic substance melt with gumminess;
(2) water soluble organic substance is positioned on three-roll grinder roller, the roller of heating three-roll grinder, the softening temperature of water soluble organic substance to be achieved, the obtained water soluble organic substance melt as sizing agent, bring into operation three-roll grinder, treats that water soluble organic substance melt is laid on the roller of three-roll grinder, more slowly add graphite, three-roll grinder continues operation and carries out grinding stripping to the graphite added, and obtains Graphene and water soluble organic substance melted blend;
(3) Graphene step (2) obtained and water soluble organic substance melted blend are immersed in distilled water, wash 3-5 time, to remove water soluble organic substance, namely obtain Graphene.
2. the green method preparing Graphene on a large scale according to claim 1, it is characterized in that, described water soluble organic substance adopts one or more the mixture in water-soluble monose, disaccharides, oligose, any two kinds and above mixing time be any proportioning.
3. the green method preparing Graphene on a large scale according to claim 2, is characterized in that, described water-soluble monose adopts glucose, fructose, semi-lactosi, sorbose, tagatose, inositol or seminose; Described water-soluble disaccharides adopts sucrose, lactose or maltose; Described water soluble oligosaccharide adopts raffinose, wood sugar, trehalose, stachyose, cyclodextrine, malto-oligosaccharide, fructose oligosaccharides or soybean oligosaccharide.
4. the green method preparing Graphene on a large scale according to claim 1, it is characterized in that, described graphite is one or more the mixture in natural graphite, expanded graphite, high orientation graphite and thermo-cracking graphite, any two kinds and above mixing time be any proportioning.
5. the green method preparing Graphene on a large scale according to claim 1, is characterized in that, in described step (2), the time that three-roll grinder peels off graphite is 0.5 ~ 72h.
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| CN106365156A (en) * | 2016-08-28 | 2017-02-01 | 桂林新艺制冷设备有限责任公司 | Method for preparing graphene |
| CN106564884A (en) * | 2017-01-19 | 2017-04-19 | 成都新柯力化工科技有限公司 | Method for preparing graphene through mechanical stretching |
| CN107055519A (en) * | 2016-12-28 | 2017-08-18 | 成都新柯力化工科技有限公司 | A kind of method peeled off and prepare graphene microchip that rubbed using three-roll grinder in the same direction |
| CN107140628A (en) * | 2017-07-03 | 2017-09-08 | 北京旭碳新材料科技有限公司 | Modified graphene slurry and preparation method thereof |
| CN108163847A (en) * | 2018-01-12 | 2018-06-15 | 昂星新型碳材料常州有限公司 | The preparation method of large stretch of diameter graphene and large stretch of diameter graphene |
| CN108328603A (en) * | 2017-01-20 | 2018-07-27 | 清华大学 | The transfer method of nano material based on sugar |
| CN108675288A (en) * | 2018-07-25 | 2018-10-19 | 恒力（厦门）石墨烯科技产业集团有限公司 | A kind of method that Mechanical Method prepares high purity graphite alkene microplate |
| CN108996495A (en) * | 2018-09-29 | 2018-12-14 | 深圳市通产丽星股份有限公司 | A kind of nano-graphene microplate and preparation method thereof |
| CN109019577A (en) * | 2018-09-29 | 2018-12-18 | 深圳市通产丽星股份有限公司 | A kind of graphene and preparation method thereof |
| CN110040727A (en) * | 2019-05-15 | 2019-07-23 | 华侨大学 | A kind of continuous strip preparation method of graphene film |
| CN110143586A (en) * | 2019-03-26 | 2019-08-20 | 上海烯望材料科技有限公司 | A kind of preparation method of the graphene of single layer or few layer |
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| CN111847433A (en) * | 2020-06-29 | 2020-10-30 | 深圳石墨烯创新中心有限公司 | Method for preparing graphene by using three-roller grinding machine |
| CN115611271A (en) * | 2022-10-28 | 2023-01-17 | 中国科学院福建物质结构研究所 | Preparation method of graphene |
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| US10472243B2 (en) | 2015-09-25 | 2019-11-12 | Su-Zhou Cstar Material Technology Co., Ltd | Industrial method for preparing large-sized graphene |
| CN106365156A (en) * | 2016-08-28 | 2017-02-01 | 桂林新艺制冷设备有限责任公司 | Method for preparing graphene |
| CN106365156B (en) * | 2016-08-28 | 2018-07-06 | 桂林新艺制冷设备有限责任公司 | A kind of method for preparing graphene |
| CN107055519A (en) * | 2016-12-28 | 2017-08-18 | 成都新柯力化工科技有限公司 | A kind of method peeled off and prepare graphene microchip that rubbed using three-roll grinder in the same direction |
| CN106564884A (en) * | 2017-01-19 | 2017-04-19 | 成都新柯力化工科技有限公司 | Method for preparing graphene through mechanical stretching |
| CN108328603A (en) * | 2017-01-20 | 2018-07-27 | 清华大学 | The transfer method of nano material based on sugar |
| CN107140628A (en) * | 2017-07-03 | 2017-09-08 | 北京旭碳新材料科技有限公司 | Modified graphene slurry and preparation method thereof |
| CN108163847A (en) * | 2018-01-12 | 2018-06-15 | 昂星新型碳材料常州有限公司 | The preparation method of large stretch of diameter graphene and large stretch of diameter graphene |
| CN108163847B (en) * | 2018-01-12 | 2020-04-17 | 昂星新型碳材料常州有限公司 | Preparation method of large-sheet-diameter graphene and large-sheet-diameter graphene |
| CN108675288A (en) * | 2018-07-25 | 2018-10-19 | 恒力（厦门）石墨烯科技产业集团有限公司 | A kind of method that Mechanical Method prepares high purity graphite alkene microplate |
| CN108996495A (en) * | 2018-09-29 | 2018-12-14 | 深圳市通产丽星股份有限公司 | A kind of nano-graphene microplate and preparation method thereof |
| CN109019577A (en) * | 2018-09-29 | 2018-12-18 | 深圳市通产丽星股份有限公司 | A kind of graphene and preparation method thereof |
| CN110143586A (en) * | 2019-03-26 | 2019-08-20 | 上海烯望材料科技有限公司 | A kind of preparation method of the graphene of single layer or few layer |
| CN110143586B (en) * | 2019-03-26 | 2021-04-02 | 中科悦达(上海)材料科技有限公司 | Preparation method of single-layer or few-layer graphene |
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| CN110040727B (en) * | 2019-05-15 | 2022-07-29 | 华侨大学 | Continuous stripping preparation method of graphene sheet |
| CN111847433A (en) * | 2020-06-29 | 2020-10-30 | 深圳石墨烯创新中心有限公司 | Method for preparing graphene by using three-roller grinding machine |
| CN115611271A (en) * | 2022-10-28 | 2023-01-17 | 中国科学院福建物质结构研究所 | Preparation method of graphene |
| CN115611271B (en) * | 2022-10-28 | 2024-02-23 | 中国科学院福建物质结构研究所 | Preparation method of graphene |
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