CN104150471B - A kind of method of redox graphene - Google Patents
A kind of method of redox graphene Download PDFInfo
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Abstract
The invention discloses a kind of method of redox graphene, belong to technical field of graphene, to solve the method high toxicity of redox graphene in prior art, high pollution, high energy consumption, the cycle is long, reduction effect is poor problem.The method of redox graphene of the present invention, comprises the following steps: the organic solvent 1) adding solubilized halogen simple substance in the aqueous dispersions of 0.1 ~ 5mg/mL graphene oxide, ultrasonic disperse; 2) haloid acid is added, back flow reaction 1 ~ 4h at 60 ~ 100 DEG C; 3) while hot suction filtration and wash, dry, obtain the Graphene after reduction.The inventive method technique is simple, the cycle is short, reduction effect good (C/O reaches 19.7 ~ 21.9), and the continuous industry being easy to realize redox graphene is produced, and is a kind of method of low power consuming, oligosaprobic environmentally friendly redox graphene.
Description
Technical field
The present invention relates to technical field of graphene, particularly a kind of method of redox graphene.
Background technology
Graphene is the novel material of the individual layer sheet structure be made up of carbon atom, is a kind ofly to form with SP2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.Graphene is considered to hypothetical structure always, cannot stable existence separately, until English physicist success in 2004 isolates Graphene from graphite, and confirms that it can Individual existence.Graphene is known the hardest the thinnest nano material, and it is almost completely transparent, only absorbs the light of 2.3%, thermal conductivity is higher than carbon nanotube and diamond, under normal temperature, its electronic mobility is than CNT (carbon nano-tube) or silicon wafer height, and resistivity, than copper or silver-colored low, is the material that resistivity is minimum.Because its resistivity is extremely low, electron transfer rate is exceedingly fast, and is suitable for doing electronic component or transistor, is also applicable to making transparent touch screen, tabula rasa even solar cell.
At present, redox graphene is the generally acknowledged approach that can obtain Graphene at a low price in a large number.The shortcomings such as and the method for reducing of graphene oxide mainly comprises hydrazine hydrate reduction, high-temperature hot reduction etc. in prior art, these methods have high toxicity, high pollution, high energy consumption, and preparation cycle is long, reduction effect difference.Therefore, for accelerating to realize the suitability for industrialized production of grapheme material, develop a kind of less energy-consumption, low stain, the method for efficient, fast restore graphene oxide.
Summary of the invention
The invention provides a kind of method of redox graphene, to solve the method high toxicity of redox graphene in prior art, high pollution, high energy consumption, the cycle is long, reduction effect is poor problem.
Technical scheme of the present invention is:
A method for redox graphene, comprises the following steps:
1) in the aqueous dispersions of 0.1 ~ 5mg/mL graphene oxide, the organic solvent of solubilized halogen simple substance is added, ultrasonic disperse;
2) haloid acid is added, back flow reaction 1 ~ 4h at 60 ~ 100 DEG C;
3) while hot suction filtration and wash, dry, obtain the Graphene after reduction.
Surface of graphene oxide is containing abundant oxygen functional group, and be easily scattered in water, organic solvent directly dilutes the aqueous dispersions of graphene oxide, and make graphene oxide dispersion effect better, graphene oxide can be reduced more fully; In addition, graphene oxide is by haloid acid reduction process, and the halogen simple substance of generation is dissolved in this organic solvent fast, prevents poisonous halogen simple substance from evaporateing in air to a certain extent.
Step 2) in, reaction process adopts condensing reflux system, can guarantee that each concentration of component of reaction system is constant on the one hand, prevent harmful by-products halogen simple substance from evaporateing in air, atmosphere pollution simultaneously.
Preferably, the aqueous dispersions preparation process of graphene oxide described in step 1) is as follows: mixed in a kettle. with the nitration mixture that 4 ~ 6L is made up of the vitriol oil and strong phosphoric acid by 100 ~ 300g natural graphite, 250 ~ 750g potassium permanganate is slowly added under lower than the condition of 20 DEG C, sealed reactor, after being warming up to 75 ~ 85 DEG C of reaction 1 ~ 4h, product taken out from reactor and is diluted to 30 ~ 50L, then adding 0.5 ~ 0.7L hydrogen peroxide and obtain jonquilleous graphite oxide solution; Then with acid and the washing of water alternating centrifugal, be 5 ~ 6 to pH value of solution, remove foreign ion; Finally, ultrasonic disperse, the aqueous dispersions of preparation finite concentration graphene oxide; In wherein said nitration mixture, the volume ratio of the vitriol oil and strong phosphoric acid is 9:1 ~ 7:3.Take a morsel the aqueous dispersions of described graphene oxide, lyophilize, grind, sieve to obtain graphene oxide powder, after tested, the obtained graphene oxide C/O ratio of present method is 2.0 ~ 2.2;
Preferably, organic solvent described in step 1) is at least one in Glacial acetic acid, dehydrated alcohol, ether, chloroform, tetracol phenixin.
Preferably, organic solvent described in step 1) is Glacial acetic acid or dehydrated alcohol.There is good solvability to halogen simple substance, dissolve each other with water, and Glacial acetic acid and dehydrated alcohol are all nontoxic simultaneously.
As preferably, the volume ratio of organic solvent described in step 1) and water is 0.001 ~ 100:1.
As preferably, in step 1), the concentration of the aqueous dispersions of graphene oxide is 1 ~ 2mg/mL.
As preferably, step 2) described in haloid acid be at least one in spirit of salt, Hydrogen bromide, hydroiodic acid HI.
Preferably, step 2) described in the concentration of haloid acid be 35 ~ 50%.
Beneficial effect of the present invention is:
The inventive method technique is simple, the cycle is short, reduction effect good (C/O reaches 19.7 ~ 21.9), and the continuous industry being easy to realize redox graphene is produced, and is a kind of method of low power consuming, oligosaprobic environmentally friendly redox graphene.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the x-ray diffraction pattern (XRD) of prepared sample in embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of prepared sample in embodiment 1;
Fig. 3 is the transmission electron microscope picture (TEM) of prepared sample in embodiment 1;
Fig. 4 is the XPS spectrum figure of prepared sample in embodiment 1;
Fig. 5 is the XPS spectrum figure of prepared sample in embodiment 3.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment
Embodiment 1
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide is prepared: first, 200g natural graphite and the 5L nitration mixture that is made up of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under lower than the condition of 20 DEG C, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 DEG C of reactions 2 hours, is taken out by product, add deionized water and be diluted to 40L solution, add 0.6L hydrogen peroxide and obtain glassy yellow graphite oxide solution from reactor lower end; Then, with acid (hydrochloric acid) and the washing of water alternating centrifugal, to pH value of solution=5 ~ 6, foreign ion is removed; Finally, ultrasonic disperse graphite oxide, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.After tested, the graphene oxide C/O ratio that present method is obtained is 2.1;
2) aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml is measured, add 3L Glacial acetic acid, ultrasonic disperse 1 hour, add 40ml hydroiodic acid HI (massfraction 45%) again, magnetic agitation, condensing reflux 1 hour at 100 DEG C, then suction filtration is separated, repeatedly wash through saturated sodium carbonate, acetone and deionized water, the Graphene that washed product must be reduced through lyophilize, grind the graphene powder that sieves to obtain.Analyze after tested: the specific conductivity of the Graphene after the present embodiment reduction is 9041 S/m, C/O ratio is 19.7, and specific surface area is 75.1 m
2/ g.
Embodiment 2:
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide is prepared: first, 200g natural graphite and the 5L nitration mixture that is made up of the 4.5L vitriol oil and 0.5L strong phosphoric acid to be mixed in reactor and even by automatically controlled magnetic stirrer, when slowly adding 500g potassium permanganate lower than when 20 DEG C; Afterwards, sealed reactor is also warming up to 75 DEG C of reactions 4 hours, is taken out by product, be diluted to 40L solution, add 0.6L hydrogen peroxide and obtain glassy yellow graphite oxide solution from reactor lower end; Then, with acid (sulfuric acid) and the washing of water alternating centrifugal, to pH value of solution=5 ~ 6, foreign ion is removed; Finally, ultrasonic disperse graphite oxide, makes the graphene oxide solution that concentration is 2.0mg/ml.After tested, the graphene oxide C/O ratio that present method is obtained is 2.0;
2) aqueous dispersions that 1L concentration is 2.0mg/ml graphene oxide is measured, add 3L Glacial acetic acid, ultrasonic disperse 1 hour, add 40ml hydroiodic acid HI (massfraction 45%) again, magnetic agitation, condensing reflux 4 hours at 60 DEG C, then suction filtration is separated, repeatedly wash through saturated sodium carbonate, acetone and deionized water, the Graphene that washed product must be reduced through lyophilize.Analyze known after tested: the specific conductivity of the Graphene after reduction is 6338 S/m.
Embodiment 3
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide is prepared: first, 200g natural graphite and the 5L nitration mixture that is made up of the 4.5L vitriol oil and 0.5L strong phosphoric acid to be mixed in reactor and even by automatically controlled magnetic stirrer, when slowly adding 500g potassium permanganate lower than when 20 DEG C; Afterwards, sealed reactor is also warming up to 85 DEG C of reactions 1 hour, is taken out by product, be diluted to 40L solution, add 0.6L hydrogen peroxide and obtain glassy yellow graphite oxide solution from reactor lower end; Then, with acid and the washing of water alternating centrifugal, to pH value of solution=5 ~ 6, foreign ion is removed; Finally, ultrasonic disperse graphite oxide, makes the graphene oxide solution that concentration is 5.0mg/ml.After tested, the graphene oxide C/O ratio that present method is obtained is 2.2;
2) aqueous dispersions that 1L concentration is the graphene oxide of 5.0mg/ml is measured, add 1.5L dehydrated alcohol, ultrasonic 1 hour, be transferred in 5L three-necked bottle, under electric stirring condition, add 1.5L spirit of salt (massfraction is 36% ~ 38%) and 40ml hydroiodic acid HI (massfraction 45%), at 90 DEG C, condensing reflux reacts 3 hours, then 30min is left standstill, suction filtration while hot, then suction filtration is separated, and repeatedly washs through saturated sodium carbonate, acetone and water, washed product is through lyophilize, and ground sieve series obtains graphene powder.Analyze after tested: the specific conductivity of graphene powder is 7163 S/m, C/O ratio is 21.9, and specific surface area is 61.0 m
2/ g.
Embodiment 4
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide is prepared: first, 125g natural graphite and the 2L nitration mixture that is made up of the 1.7L vitriol oil and 0.3L strong phosphoric acid to be mixed in reactor and even by automatically controlled magnetic stirrer, when slowly adding 200g potassium permanganate lower than when 20 DEG C; Afterwards, sealed reactor is also warming up to 80 DEG C of reactions 2 hours, is taken out by product, be diluted to 40L solution, add 0.6L hydrogen peroxide and obtain glassy yellow graphite oxide solution from reactor lower end; Then, with acid (hydrochloric acid) and the washing of water alternating centrifugal, to pH value of solution=5 ~ 6, foreign ion is removed; Finally, ultrasonic disperse graphite oxide, makes the graphene oxide solution that concentration is 2.0mg/ml.After tested, the graphene oxide C/O ratio that present method is obtained is 2.1;
2) aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml is measured, add 1.5L dehydrated alcohol, ultrasonic 1 hour, be transferred in 5L three-necked bottle, under electric stirring condition, add 1.5L spirit of salt (massfraction is 36% ~ 38%) and 40ml hydroiodic acid HI (massfraction 45%), at 90 DEG C, condensing reflux reaction 1.5h, then leaves standstill 30 minutes, suction filtration while hot, use saturated sodium bicarbonate, acetone and deionized water wash successively, last lyophilize, ground sieve series obtains graphene powder.Analyze specific conductivity about 6852 S/m of known graphene powder after tested.
Embodiment 5:
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide is prepared: first, 200g natural graphite and the 5L nitration mixture that is made up of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under lower than the condition of 20 DEG C, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 DEG C of reactions 2 hours, is taken out by product, add deionized water and be diluted to 40L solution, add 0.6L hydrogen peroxide and obtain glassy yellow graphite oxide solution from reactor lower end; Then, with acid (hydrochloric acid) and the washing of water alternating centrifugal, to pH value of solution=5 ~ 6, foreign ion is removed; Finally, ultrasonic disperse graphite oxide, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.
2) aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml is measured, add 1.5L dehydrated alcohol, ultrasonic 1 hour, be transferred in 5L three-necked bottle, under electric stirring condition, add 1.5L spirit of salt (massfraction is 36% ~ 38%) and 40ml hydroiodic acid HI (massfraction 45%), at 60 DEG C, condensing reflux reacts 3 hours, then leaves standstill 30 minutes, suction filtration while hot, use saturated sodium bicarbonate, acetone and deionized water wash successively, last lyophilize, ground sieve series obtains graphene powder.Analyze specific conductivity about 5479 S/m of known graphene powder after tested.
Embodiment 6:
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide is prepared: first, 200g natural graphite and the 5L nitration mixture that is made up of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under lower than the condition of 20 DEG C, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 DEG C of reactions 2 hours, is taken out by product, add deionized water and be diluted to 40L solution, add 0.6L hydrogen peroxide and obtain glassy yellow graphite oxide solution from reactor lower end; Then, with acid (hydrochloric acid) and the washing of water alternating centrifugal, to pH value of solution=5 ~ 6, foreign ion is removed; Finally, ultrasonic disperse graphite oxide, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.
2) aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml is measured, add 1.5L dehydrated alcohol, ultrasonic 1 hour, be transferred in 5L three-necked bottle, under electric stirring condition, add 1.5L spirit of salt (massfraction is 36% ~ 38%) and 20ml hydroiodic acid HI (massfraction 45%), at 90 DEG C, condensing reflux reaction 3h, then leaves standstill 30 minutes, suction filtration while hot, use saturated sodium bicarbonate, acetone and deionized water wash successively, last lyophilize, ground sieve series obtains graphene powder.Analyze specific conductivity about 6299 S/m of known graphene powder after tested.
Comparative example 1
The method of reducing of the graphene oxide of this comparative example comprises the following steps:
1) aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide is prepared: first, 200g natural graphite and the 5L nitration mixture that is made up of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under lower than the condition of 20 DEG C, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 DEG C of reactions 2 hours, is taken out by product, add deionized water and be diluted to 40L solution, add 0.6L hydrogen peroxide and obtain glassy yellow graphite oxide solution from reactor lower end; Then, with acid (hydrochloric acid) and the washing of water alternating centrifugal, to pH value of solution=5 ~ 6, foreign ion is removed; Finally, ultrasonic disperse graphite oxide, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.
2) aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml is measured, add 40ml hydroiodic acid HI (massfraction 45%), magnetic agitation, condensing reflux 1 hour at 100 DEG C, then suction filtration is separated, repeatedly wash through saturated sodium carbonate, acetone and deionized water, the Graphene that washed product must be reduced through lyophilize, grind the graphene powder that sieves to obtain.Analyze after tested: the specific conductivity of the Graphene after the present embodiment reduction is 740 S/m, C/O ratio is 7.6, and specific surface area is 18.5m
2/ g.
Comparative example 1 is only the dispersion agent of graphene oxide with the difference of embodiment 1, and in embodiment 1, the dispersion agent of graphene oxide is water/Glacial acetic acid, and in comparative example 1, the dispersion agent of graphene oxide is only water.This comparative example illustrates, adds the aqueous dispersions that organic solvent disperses graphene oxide further, most important to the reduction of graphene oxide, and its effect clearly.
Comparative example 2
The method of reducing of the graphene oxide of this comparative example comprises the following steps:
1) aqueous dispersions (adopting general hummers method) of graphene oxide is prepared, step is as follows: under condition of ice bath, 50g natural graphite mixes with 25g SODIUMNITRATE, adds the 1.15L vitriol oil, then adds 150g potassium permanganate, react 2 hours, be warming up to 35 DEG C of reactions 50 minutes, add deionized water 0.75L afterwards, keep 20-30 minute at 90-100 DEG C, then add the deionized water of 0.15L hydrogen peroxide and 7L, obtain glassy yellow graphite oxide solution; Afterwards, adopt sulphuric acid soln and the deionized water alternating centrifugal of 5%, to sulfate radical-free ion, pH=5 ~ 6; Finally, supersound process, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.After tested, the graphene oxide C/O ratio that present method is obtained is 2.1;
2) aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml is measured, add 3L Glacial acetic acid, ultrasonic disperse 1 hour, add 40ml hydroiodic acid HI (massfraction 45%) again, magnetic agitation, condensing reflux 1 hour at 100 DEG C, then suction filtration is separated, repeatedly wash through saturated sodium carbonate, acetone and deionized water, the Graphene that washed product must be reduced through lyophilize, grind the graphene powder that sieves to obtain.Analyze after tested: the specific conductivity of the Graphene after the present embodiment reduction is 6845S/m, C/O ratio is 17.6, and specific surface area is 58.6 m
2/ g.
From the difference of embodiment 1, comparative example 2 is only that the preparation method of the aqueous dispersions of graphene oxide is different, the airtight legal system of the phosphoric acid that embodiment 1 adopts oneself to research and develop is standby, and prior art adopts general hummers method.The Advantages found of the airtight method of phosphoric acid exists: 1) phosphoric acid has the effect of protection lamella, reduces the vitriol oil to the destruction of lamella; 2) graphene oxide that oxidation is obtained is more homogeneous; 3) technique is simple, solves the problem of hummers method temperature control complexity.Although the obtained graphene oxide C/O difference of two kinds of methods is little, the obtained graphene oxide of the airtight method of phosphoric acid is more homogeneous, therefore with the standby graphene oxide of the airtight legal system of phosphoric acid for Graphene is prepared in raw material reduction, effect is better.
Because gained Graphene performance is similar, existing for the present embodiment 1, be analyzed as follows:
The x-ray diffraction pattern (XRD) of prepared sample in Fig. 1, the broad peak between 20-27 degree shows that this sample is grapheme material;
The scanning electron microscope (SEM) photograph (SEM) of prepared Graphene sample in Fig. 2, known graphene powder is made up of the micro-nano sheet structure of puffy;
The transmission electron microscope picture (TEM) of prepared Graphene sample in Fig. 3, the microtexture of known graphene powder comprises micro-nano of a large amount of thin layer.
Claims (5)
1. a method for redox graphene, is characterized in that, comprises the following steps:
1) in the aqueous dispersions of 0.1 ~ 5mg/mL graphene oxide, the organic solvent of solubilized halogen simple substance is added, ultrasonic disperse; Described organic solvent is at least one in Glacial acetic acid, dehydrated alcohol, ether, chloroform, tetracol phenixin; The aqueous dispersions preparation process of described graphene oxide is as follows: mixed in a kettle. with the nitration mixture that 4 ~ 6L is made up of the vitriol oil and strong phosphoric acid by 100 ~ 300g natural graphite, 250 ~ 750g potassium permanganate is slowly added under lower than the condition of 20 DEG C, sealed reactor, after being warming up to 75 ~ 85 DEG C of reaction 1 ~ 4h, product taken out from reactor and is diluted to 30 ~ 50L, then adding 0.5 ~ 0.7L hydrogen peroxide and obtain jonquilleous graphite oxide solution; Then with acid and the washing of water alternating centrifugal, be 5 ~ 6 to pH value of solution, remove foreign ion, ultrasonic disperse graphite oxide, the aqueous dispersions of preparation finite concentration graphene oxide; In wherein said nitration mixture, the volume ratio of the vitriol oil and strong phosphoric acid is 9:1 ~ 7:3;
2) spirit of salt, Hydrogen bromide or hydroiodic acid HI is added, back flow reaction 1 ~ 4h at 60 ~ 100 DEG C;
3) while hot suction filtration and wash, dry, obtain the Graphene after reduction.
2. the method for redox graphene as claimed in claim 1, is characterized in that: organic solvent described in step 1) is Glacial acetic acid or dehydrated alcohol.
3. the method for redox graphene as claimed in claim 1, is characterized in that: the volume ratio of organic solvent described in step 1) and water is 0.001 ~ 100:1.
4. the method for redox graphene as claimed in claim 1, is characterized in that: in step 1), the concentration of the aqueous dispersions of graphene oxide is 1 ~ 2mg/mL.
5. the method for redox graphene as claimed in claim 1, is characterized in that: step 2) described in the concentration of spirit of salt, Hydrogen bromide or hydroiodic acid HI be 35 ~ 50%.
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| CN104445168A (en) * | 2014-11-28 | 2015-03-25 | 张明 | Preparation method of graphene oxide |
| CN104556016B (en) * | 2015-01-23 | 2017-04-05 | 青岛科技大学 | A kind of low-temperature environment-friendly preparation method of Graphene |
| CN104617300A (en) * | 2015-02-09 | 2015-05-13 | 天津师范大学 | Method for preparing lithium ion battery anode/cathode material from reduced graphene oxide |
| CN105000554A (en) * | 2015-08-22 | 2015-10-28 | 赵兵 | Graphene oxide reduction method |
| CN105129782A (en) * | 2015-08-22 | 2015-12-09 | 钱景 | Method for reducing graphene oxide |
| CN105197918A (en) * | 2015-10-12 | 2015-12-30 | 湖北工业大学 | High-quality graphene and quick preparation method thereof |
| WO2017083566A1 (en) * | 2015-11-12 | 2017-05-18 | Cornell University | High performance electrodes |
| CN106115676B (en) * | 2016-06-28 | 2018-11-20 | 常州第六元素材料科技股份有限公司 | A kind of graphene organic ink and preparation method thereof |
| CN106317440A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Method for preparing composite graphene heat-conducting film |
| CN106450331B (en) * | 2016-10-27 | 2019-02-05 | 萝北奥星新材料有限公司 | The method for preparing graphene conductive agent slurry with graphite tailing |
| CN106521719A (en) * | 2016-11-10 | 2017-03-22 | 过冬 | Graphene-based carbon nanofiber preparation method |
| CN107117599B (en) * | 2017-04-19 | 2020-11-13 | 东华大学 | Preparation method of chloro-hybrid graphene |
| CN111847434A (en) * | 2020-07-30 | 2020-10-30 | 德州智南针机械科技有限公司 | Preparation process of environment-friendly graphene |
| CN113929090A (en) * | 2021-12-03 | 2022-01-14 | 曲靖华金雨林科技有限责任公司 | Preparation method of graphene |
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| CN102275902A (en) * | 2010-06-12 | 2011-12-14 | 中国科学院金属研究所 | Method for preparing graphene material by reducing graphene oxide |
| CN103723709A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of aqueous single-layer graphene solution |
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