CN104150471A - Method for reducing graphene oxide - Google Patents
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- CN104150471A CN104150471A CN201410370975.3A CN201410370975A CN104150471A CN 104150471 A CN104150471 A CN 104150471A CN 201410370975 A CN201410370975 A CN 201410370975A CN 104150471 A CN104150471 A CN 104150471A
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Abstract
The invention discloses a method for reducing graphene oxide, belong to the technical field of graphene and aiming at solving the problems of high toxicity, high pollution, high energy consumption, long period and poor reduction effect existing in the methods for reducing graphene oxide in the prior art. The method for reducing graphene oxide comprises the following steps: (1) adding an organic solvent capable of dissolving halogen element in an aqueous dispersion of 0.1-5mg/mL graphene oxide for ultrasonic dispersion; (2) undergoing reflux reaction for 1-4 hours under 60-100 DEG C by adding halogen acid; and (3) undergoing hot filtration, washing, drying to obtain reduced graphene. The method is simple, has short period and good reduction effect (C/O reaches 19.7-21.9), easily achieves the continuous industrial production of reducing graphene oxide, and is a low-energy-consumption, low-pollution and environment-friendly method for reducing graphene oxide.
Description
Technical field
The present invention relates to Graphene technical field, particularly a kind of method of redox graphene.
Background technology
Graphene is the novel material of the individual layer sheet structure that consists of carbon atom, is a kind ofly by carbon atom, with SP2 hybridized orbital, to form the flat film that hexangle type is honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Graphene is considered to hypothetical structure always, and stable existence, until Graphene is isolated in English physicist success in 2004 from graphite, and confirms that it can Individual existence separately.Graphene is known the hardest the thinnest nano material, and it is almost completely transparent, only absorbs 2.3% light, thermal conductivity is higher than carbon nanotube and diamond, its electronic mobility ratio nano carbon pipe or silicon wafer height under normal temperature, resistivity is lower than copper or silver, is the material of resistivity minimum.Because its resistivity is extremely low, electronic migration speed is exceedingly fast, and is suitable for doing electronic component or transistor, is also applicable to making even solar cell of transparent touch screen, tabula rasa.
At present, redox graphene is the approach that can obtain in a large number at a low price Graphene of generally acknowledging.And the method for reducing of graphene oxide mainly comprises hydrazine hydrate reduction, high temperature thermal reduction etc. in prior art, these methods have high toxicity, high pollution, high energy consumption, the shortcoming such as preparation cycle is long, and reduction effect is poor.Therefore, for accelerating to realize the suitability for industrialized production of grapheme material, develop a kind of less energy-consumption, low pollution, 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 problem that method high toxicity, high pollution, high energy consumption, cycle are long, reduction effect is poor of redox graphene in prior art.
Technical scheme of the present invention is:
A method for redox graphene, comprises the following steps:
1) to the organic solvent that adds solubilized halogen simple substance in the aqueous dispersions of 0.1 ~ 5mg/mL graphene oxide, ultrasonic dispersion;
2) add haloid acid, back flow reaction 1 ~ 4h at 60 ~ 100 ℃;
3) suction filtration washing, dry while hot, obtains the Graphene after reduction.
Graphene oxide surface, containing abundant oxygen functional group, is easily scattered in water, and organic solvent directly dilutes the aqueous dispersions of graphene oxide, makes graphene oxide dispersion effect better, and 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 that to a certain extent poisonous halogen simple substance from evaporateing in air.
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, has prevented that toxic byproduct halogen simple substance from evaporateing in air, atmosphere pollution simultaneously.
Preferably, described in step 1), the aqueous dispersions preparation process of graphene oxide is as follows: 100 ~ 300g natural graphite is mixed in reactor with the nitration mixture that 4 ~ 6L is comprised of the vitriol oil and strong phosphoric acid, under the condition lower than 20 ℃, slowly add 250 ~ 750g potassium permanganate, sealed reactor, be warming up to after 75 ~ 85 ℃ of reaction 1 ~ 4h, product is taken out and be diluted to 30 ~ 50L from reactor, then add 0.5 ~ 0.7L hydrogen peroxide to obtain jonquilleous graphite oxide solution; Then with acid and water, replace centrifuge washing, to pH value of solution be 5 ~ 6, removal foreign ion; Finally, ultrasonic dispersion, 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.The take a morsel aqueous dispersions of described graphene oxide, lyophilize, the graphene oxide powder that grinds, sieves and to obtain, after tested, the graphene oxide C/O ratio that present method makes 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.Halogen simple substance is had to good solvability, dissolves each other with water simultaneously, and Glacial acetic acid and dehydrated alcohol all nontoxic.
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 is at least one in spirit of salt, Hydrogen bromide, hydroiodic acid HI.
Preferably, the concentration of haloid acid step 2) is 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), is easy to realize the continuous industry production of redox graphene, 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, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
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
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining 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) prepare the aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under the condition lower than 20 ℃, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, adds deionized water and is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5 ~ 6, remove foreign ion; Finally, ultrasonic dispersion 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 makes is 2.1;
2) measure the aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml, add 3L Glacial acetic acid, ultrasonic dispersion 1 hour, add again 40ml hydroiodic acid HI (massfraction 45%), magnetic agitation, at 100 ℃, condensing reflux is 1 hour, then suction filtration is separated, through saturated sodium carbonate, acetone and deionized water, repeatedly wash, the Graphene that washed product must be reduced through lyophilize, grinds 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, and 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) prepare the aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 75 ℃ of reactions 4 hours, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (sulfuric acid) and water, replace centrifuge washing, to pH value of solution=5 ~ 6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, making concentration is the graphene oxide solution of 2.0mg/ml.After tested, the graphene oxide C/O ratio that present method makes is 2.0;
2) measure the aqueous dispersions that 1L concentration is 2.0mg/ml graphene oxide, add 3L Glacial acetic acid, ultrasonic dispersion 1 hour, add again 40ml hydroiodic acid HI (massfraction 45%), magnetic agitation, at 60 ℃, condensing reflux is 4 hours, and then suction filtration is separated, through saturated sodium carbonate, acetone and deionized water, repeatedly wash the Graphene that washed product must be reduced through lyophilize.Analyze after tested known: 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) prepare the aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 85 ℃ of reactions 1 hour, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid and water, replace centrifuge washing, to pH value of solution=5 ~ 6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, making concentration is the graphene oxide solution of 5.0mg/ml.After tested, the graphene oxide C/O ratio that present method makes is 2.2;
2) measure the aqueous dispersions that 1L concentration is the graphene oxide of 5.0mg/ml, 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 ℃, condensing reflux reaction is 3 hours, then standing 30min, suction filtration while hot, then suction filtration is separated, through saturated sodium carbonate, acetone and water, repeatedly washs, washed product is through lyophilize, and grinding sieves makes graphene powder.Analyze after tested: the specific conductivity of graphene powder is 7163 S/m, and 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) prepare the aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide: first, 125g natural graphite and the 2L nitration mixture that is comprised of the 1.7L vitriol oil and 0.3L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 200g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5 ~ 6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, making concentration is the graphene oxide solution of 2.0mg/ml.After tested, the graphene oxide C/O ratio that present method makes is 2.1;
2) measure the aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml, 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%), condensing reflux reaction 1.5h at 90 ℃, then standing 30 minutes, suction filtration while hot, use successively saturated sodium bicarbonate, acetone and deionized water wash, last lyophilize, grinding sieves makes graphene powder.Analyze after tested specific conductivity approximately 6852 S/m of known graphene powder.
Embodiment 5:
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) prepare the aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under the condition lower than 20 ℃, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, adds deionized water and is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5 ~ 6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.
2) measure the aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml, 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%), condensing reflux reaction is 3 hours at 60 ℃, then standing 30 minutes, suction filtration while hot, use successively saturated sodium bicarbonate, acetone and deionized water wash, last lyophilize, grinding sieves makes graphene powder.Analyze after tested specific conductivity approximately 5479 S/m of known graphene powder.
Embodiment 6:
The method of reducing of the graphene oxide of the present embodiment comprises the following steps:
1) prepare the aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under the condition lower than 20 ℃, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, adds deionized water and is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5 ~ 6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.
2) measure the aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml, 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%), condensing reflux reaction 3h at 90 ℃, then standing 30 minutes, suction filtration while hot, use successively saturated sodium bicarbonate, acetone and deionized water wash, last lyophilize, grinding sieves makes graphene powder.Analyze after tested specific conductivity approximately 6299 S/m of known graphene powder.
Comparative example 1
The method of reducing of the graphene oxide of this comparative example comprises the following steps:
1) prepare the aqueous dispersions (adopting the airtight legal system of phosphoric acid of independent research for graphene oxide) of graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor, and even by automatically controlled magnetic stirrer, under the condition lower than 20 ℃, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, adds deionized water and is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5 ~ 6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, makes the aqueous dispersions that concentration is the graphene oxide of 2.0mg/ml.
2) measure the aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml, add 40ml hydroiodic acid HI (massfraction 45%), magnetic agitation, at 100 ℃, condensing reflux is 1 hour, then suction filtration is separated, through saturated sodium carbonate, acetone and deionized water, repeatedly wash, the Graphene that washed product must be reduced through lyophilize, grinds 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, and C/O ratio is 7.6, and specific surface area is 18.5m
2/ g.
The difference of comparative example 1 and embodiment 1 is only the dispersion agent of graphene oxide, 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 explanation, adds organic solvent further to disperse the aqueous dispersions of graphene oxide, and most important to the reduction of graphene oxide, its effect is very obvious.
Comparative example 2
The method of reducing of the graphene oxide of this comparative example comprises the following steps:
1) prepare the aqueous dispersions (adopting general hummers method) of graphene oxide, 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 ℃ of reactions 50 minutes, add afterwards deionized water 0.75L, at 90-100 ℃, keep 20-30 minute, then the deionized water that adds 0.15L hydrogen peroxide and 7L, obtains glassy yellow graphite oxide solution; Afterwards, sulphuric acid soln and the deionized water of employing 5% are alternately centrifugal, 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 makes is 2.1;
2) measure the aqueous dispersions that 1L concentration is the graphene oxide of 2.0mg/ml, add 3L Glacial acetic acid, ultrasonic dispersion 1 hour, add again 40ml hydroiodic acid HI (massfraction 45%), magnetic agitation, at 100 ℃, condensing reflux is 1 hour, then suction filtration is separated, through saturated sodium carbonate, acetone and deionized water, repeatedly wash, the Graphene that washed product must be reduced through lyophilize, grinds the graphene powder that sieves to obtain.Analyze after tested: the specific conductivity of the Graphene after the present embodiment reduction is 6845S/m, and C/O ratio is 17.6, and specific surface area is 58.6 m
2/ g.
Comparative example 2 and the difference of embodiment 1 are only that the preparation method of aqueous dispersions of graphene oxide is different, and embodiment 1 adopts the own airtight legal system of phosphoric acid of researching and developing standby, and prior art adopts general hummers method.The advantage of the airtight method of phosphoric acid is embodied in: 1) phosphoric acid has the effect of protection lamella, reduces the destruction of the vitriol oil to lamella; 2) graphene oxide that oxidation makes is homogeneous more; 3) technique is simple, has solved the problem of hummers method temperature control complexity.Although the graphene oxide C/O difference that two kinds of methods make is little, the graphene oxide that the airtight method of phosphoric acid makes is homogeneous more, and the standby graphene oxide of the airtight legal system of phosphoric acid of therefore take is prepared Graphene as raw material reduction, and effect is better.
Because gained Graphene performance is similar, now take the present embodiment 1 as example, be analyzed as follows:
The x-ray diffraction pattern of prepared sample (XRD) in Fig. 1, the broad peak between 20-27 degree shows that this sample is grapheme material;
The scanning electron microscope (SEM) photograph of prepared Graphene sample (SEM) in Fig. 2, known graphene powder is comprised of the micro-nano sheet structure of puffy;
The transmission electron microscope picture of prepared Graphene sample (TEM) in Fig. 3, the microtexture of known graphene powder comprises micro-nano of a large amount of thin layer.
Claims (8)
1. a method for redox graphene, is characterized in that, comprises the following steps:
1) to the organic solvent that adds solubilized halogen simple substance in the aqueous dispersions of 0.1 ~ 5mg/mL graphene oxide, ultrasonic dispersion;
2) add haloid acid, back flow reaction 1 ~ 4h at 60 ~ 100 ℃;
3) suction filtration washing, dry while hot, obtains the Graphene after reduction.
2. the method for redox graphene as claimed in claim 1, it is characterized in that, described in step 1), the aqueous dispersions preparation process of graphene oxide is as follows: 100 ~ 300g natural graphite is mixed in reactor with the nitration mixture that 4 ~ 6L is comprised of the vitriol oil and strong phosphoric acid, under the condition lower than 20 ℃, slowly add 250 ~ 750g potassium permanganate, sealed reactor, be warming up to after 75 ~ 85 ℃ of reaction 1 ~ 4h, product is taken out and be diluted to 30 ~ 50L from reactor, then add 0.5 ~ 0.7L hydrogen peroxide to obtain jonquilleous graphite oxide solution; Then with acid and water, replace centrifuge washing, to pH value of solution be 5 ~ 6, removal foreign ion, ultrasonic dispersion graphite oxide, prepares the aqueous dispersions of 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.
3. the method for redox graphene as claimed in claim 1, is characterized in that: organic solvent described in step 1) is at least one in Glacial acetic acid, dehydrated alcohol, ether, chloroform, tetracol phenixin.
4. the method for the redox graphene as described in claim 1 or 3, is characterized in that: organic solvent described in step 1) is Glacial acetic acid or dehydrated alcohol.
5. the method for the redox graphene as described in claim 1 or 3, is characterized in that: the volume ratio of organic solvent described in step 1) and water is 0.001 ~ 100:1.
6. 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.
7. the method for redox graphene as claimed in claim 1, is characterized in that: step 2) described in haloid acid be at least one in spirit of salt, Hydrogen bromide, hydroiodic acid HI.
8. the method for the redox graphene as described in claim 1 or 7, is characterized in that: step 2) described in the concentration of haloid acid be 35 ~ 50%.
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| CN105197918A (en) * | 2015-10-12 | 2015-12-30 | 湖北工业大学 | High-quality graphene and quick preparation method thereof |
| US20180331365A1 (en) * | 2015-11-12 | 2018-11-15 | Cornell University | High performance electrodes |
| US10971729B2 (en) * | 2015-11-12 | 2021-04-06 | Cornell University | High performance electrodes |
| CN106115676A (en) * | 2016-06-28 | 2016-11-16 | 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 |
| CN106450331A (en) * | 2016-10-27 | 2017-02-22 | 萝北奥星新材料有限公司 | Method for preparing graphene conducting agent slurry from graphite tailings |
| CN106521719A (en) * | 2016-11-10 | 2017-03-22 | 过冬 | Graphene-based carbon nanofiber preparation method |
| CN107117599A (en) * | 2017-04-19 | 2017-09-01 | 东华大学 | A kind of preparation method of the miscellaneous graphene of chlorine |
| 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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