CN104071782A - Preparation method of graphene - Google Patents
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Abstract
The invention discloses a preparation method of graphene. The preparation method comprises the following steps: (1) reacting graphite powder, sodium nitrate and concentrated sulfuric acid at -5 DEG C to 0 DEG C; (2) adding potassium permanganate, and reacting to prepare graphite suspension liquid; (3) adding dilute sulphuric acid and ultrasonically processing; (4) adding de-ionized water; (5) adding a hydrogen peroxide solution till all gas escapes; (6) adding hydrochloric acid, fully reacting to obtain a product, and washing the product by using the de-ionized water; (7) fully dispersing deposits in the de-ionized water; and (8) adding oxalic acid powder, and reacting to remove excessive oxalic acid. According to the preparation method, a physical process is combined with a chemical process and the intercalation and stripping degree of graphite oxide is increased, so that the preparation efficiency of graphene is improved and the yield is increased by 25%-30% in comparison with that of an oxidation-reduction process in the prior art; in addition, the preparation method achieves high-yield preparation of high-quality graphene, has the characteristics of simple process and the like and is suitable for large-scale production of multi-layer graphene, and the product performance is excellent.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene.
Background technology
Except three-layer laminated graphite, scientists finds that Tan Xi family also has the soccerballene of zero dimension, the carbon nanotube of one dimension, and the carbon material of two dimension at room temperature stable existence is a mystery always.As far back as many years ago, famous physicist Peierls and Landau propose strict two dimensional crystal in theory due to its thermodynamic instability, can not exist.1966, the Mermin-Wagner theory of Mermin and Wagner pointed out that long wavelength fluctuating also can make the two dimensional crystal of long-range order be damaged.Now, Two-dimensional Carbon material be it is believed that a just theoretical model, but this does not hinder the exploration of people to Two-dimensional Carbon materials theory and experiment, and scientists attempts obtaining stable mono-layer graphite sheet.Until 2004, scientist A. K. Geim and the K. S. Novoselov of University of Manchester successfully isolate Graphene (also referred to as mono-layer graphite) by mechanically peel method first from graphite, this discovery has shocked scientific circles, not only overthrown original perfect two dimensional crystal material can not be under non-zero absolute temperature the theory of stable existence, and excited the research interest of scientists to other two-dimensional material, enriched carbon is family member simultaneously.
Graphene, can regard the mono-layer graphite sheet being stripped from as, the two-dimensional crystal lattice being formed by the carbon atom of monoatomic layer thickness, wherein carbon atom with six-ring form periodic arrangement in Graphene plane.It is the thinnest material of finding at present, and thickness only has 0.35 nm, and carbon atom is with the mutual bonding of mode of sp2 hydridization, and the bond distance of C-C is 0.142 nm, 120 ° of bond angles.It is the elementary cell that builds other dimension carbon material, it can the bent richness that forms zero dimension (0D) of wing strangle rare (fullerene), the carbon nanotube (carbon nano-tube, CNT) that is rolled into one dimension (1D) can also pile the graphite (graphite) of three-dimensional (3D).
Just because of the two-dirnentional structure of Graphene uniqueness, make it have many special propertys such as excellent electricity, mechanics, optics and calorifics that are different from other dimension materials, thereby within several years, receive much concern at this.Research for it is not only confined to theoretical aspect at present.Graphene has been applied to the preparation of various devices, comprises low-yield highdensity electron device, senser element etc.The same with other novel materials of preparing large-scale application, the preparation of material and processing are the prerequisites that Graphene is able to practical application.From first passage micromechanics stripping method, obtain after Graphene, people have in succession proposed the methods such as epitaxy method, chemical Vapor deposition process, solvent-thermal method, electrochemical process, chemical reduction method and have prepared Graphene.Wherein, chemical reduction method is a kind of softening method that graphite is raw material of take, and by microwave or ultrasonic wave, graphite oxide is peeled off and is obtained graphene oxide solution, and then GO is carried out to chemical reduction obtain Graphene.This method be take cheap graphite as raw material, through peroxidation, peel off, reduce, easily realizes the mass production of Graphene, can meet large-scale application demand.
At present, oxidation reduction process becomes industry and prepares Graphene one of the most attractive approach so that its technique is simple, with low cost.In numerous methods of preparing graphite oxide, the technical process of Hmnmers method is simple, green, safety, thereby become, prepares at present one of the most frequently used method of graphite oxide.The method has mainly comprised low temperature, middle temperature, three step of reaction of high temperature.Research shows M:(Fu Ling, Liu Hongbo, and Zou Yanhong, Li Bo .Hummers legal system affects the technological factor research [J] of degree of oxidation during for graphite oxide. carbon element, 2005 (4): 10-14) low-temp reaction sulfuric acid molecule mainly occurs at graphite layers intercalation; The main deep oxidation that graphite occurs of middle temperature reaction; Mainly there is the hydrolysis reaction of compound in high-temperature reaction process.Low-temp reaction intercalation is abundant, and completely, pyroreaction hydrolysis thoroughly, will be one of approach obtaining the larger graphite oxide of interlamellar spacing in middle temperature reaction depth oxidation.The pyroreaction stage of Hummers method, in the higher mixed solution that contains the vitriol oil of temperature, add deionized water, can make mixed solution produce local high temperature, cause temperature of reaction to be difficult to control, the local temperature of mixed solution is too high simultaneously, the decomposes that makes sulfuric acid-compound between graphite layers, the insets such as sulfuric acid are deviate from rapidly from graphite layers, thereby have greatly affected the quality of graphite oxide.
In prior art, the method for conventionally preparing Graphene is: 1, micromechanics stripping method; 2, chemical Vapor deposition process; 3, oxidation-reduction method; 4, solvent stripping method; 5, solvent-thermal method, 6, additive method.Wherein for the 3rd kind of method, before also carried out discussion, mainly by Hummers method or improved Hummers legal system for GO, then obtain graphene oxide with reduction GO such as sodium borohydrides, it is on the low side that this method obtains the productive rate of Graphene.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Graphene.
The technical solution used in the present invention is:
A preparation method for Graphene, comprises the following steps:
The first step, under-5 ~ 0 ℃ of condition, adds Graphite Powder 99, SODIUMNITRATE in reaction vessel, then adds the vitriol oil, keeps temperature of reaction system at-5 ~ 0 ℃, and supersound process, then fully stirs;
Second step adds potassium permanganate in the first step gained solution, keeps temperature of reaction system not higher than 10 ℃, stirs 16 ~ 24h, prepares graphite suspension;
The 3rd step adds dilute sulphuric acid in graphite suspension, and then supersound process under the condition stirring, fully reacts 2 ~ 6h;
The 4th step, then add deionized water, keep temperature of reaction system not higher than 10 ℃, fully react 6 ~ 12h;
The 5th step, keeps temperature of reaction system not higher than under the condition of 10 ℃, dropwise adds superoxol, until gas is overflowed completely;
The 6th step, adds hydrochloric acid, and fully reaction, then uses reaction product deionized water centrifuge washing, and the pH of extremely last centrifugal supernatant liquid is 6.5 ~ 7.5;
The 7th step, is placed in deionized water for ultrasonic the precipitation of the 6th step gained and disperses, and after centrifugal treating, gained upper solution is graphene oxide dispersion liquid;
The 8th step adds oxalic acid powder in graphene oxide dispersion liquid, and then heating isothermal reaction under the condition stirring, reheats to remove excessive oxalic acid, obtains the graphene solution that homogeneous disperses.
In the first step, described Graphite Powder 99 is 400-600 object natural graphite powder; The mass concentration of the described vitriol oil is 68% ~ 98%.
In the first step, described supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument of ultrasonic power 120 ~ 400w and operating frequency are 20 ~ 40kHz, the alternately supersound process of the ultrasonic cell disrupte machine of ultrasonic power 800 ~ 1200w, and the total time of alternate treatment is 1 ~ 2h.
In the 3rd step, the mass concentration of described dilute sulphuric acid is 5% ~ 10%.
In the 3rd step, supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument supersound process of ultrasonic power 120 ~ 400w, and the time of processing is 0.5-1h.
In the 5th step, the mass concentration of described superoxol is 1 ~ 3%.
In the 6th step, the mass concentration of described hydrochloric acid is 5% ~ 10%.
In the 6th step, the temperature of deionized water is lower than 10 ℃, and the condition of centrifuge washing is: centrifuge speed: 8000 ~ 10000r/min; Centrifugation time 15 ~ 30min.
In the 7th step, described ultrasonic dispersion refers to that by operating frequency be 20 ~ 40kHz, and the ultrasonic disintegrator of ultrasonic power 800 ~ 1200w carries out supersound process; The time of supersound process is 0.5 ~ 2h.
The amount ratio of the deionized water in Graphite Powder 99, SODIUMNITRATE, the vitriol oil, potassium permanganate, dilute sulphuric acid, the 4th step, superoxol, hydrochloric acid is: 1g:(0.45-0.55) g:(23-25) ml:(2.5-3.5) g:(18-22) ml:(55-65) ml:(18-22) ml:(38-42) ml; Graphene dispersing solution in the 8th step, the amount ratio of oxalic acid are 20ml:(2.5-3.5) g.
The invention has the beneficial effects as follows:
The present invention, by conjunction with physics and chemical process, improves intercalation and the extent of exfoliation of graphite oxide, has improved the preparation efficiency of Graphene, than the productive rate of oxidation-reduction method of the prior art, improves 25% ~ 30%.In addition, the present invention has realized high yield and has prepared high-quality Graphene, has the features such as technique is simple, product performance are good simultaneously, is applicable to the scale operation of multi-layer graphene.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram sheet of Graphene in the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope diagram sheet of Graphene in the embodiment of the present invention 1;
Fig. 3 is the transmission electron micrograph of Graphene in the embodiment of the present invention 1.
Embodiment
The first step, under-5 ~ 0 ℃ of condition, adds Graphite Powder 99, SODIUMNITRATE in reaction vessel, then adds the vitriol oil, keeps temperature of reaction system at-5 ~ 0 ℃, and supersound process, then fully stirs;
Second step adds potassium permanganate in the first step gained solution, keeps temperature of reaction system not higher than 10 ℃, stirs 16 ~ 24h, prepares graphite suspension;
The 3rd step adds dilute sulphuric acid in graphite suspension, and then supersound process under the condition stirring, fully reacts 2 ~ 6h;
The 4th step, then add deionized water, keep temperature of reaction system not higher than 10 ℃, fully react 6 ~ 12h;
The 5th step, keeps temperature of reaction system not higher than under the condition of 10 ℃, dropwise adds superoxol, until gas is overflowed completely;
The 6th step, adds hydrochloric acid, and fully reaction, then uses reaction product deionized water centrifuge washing, and the pH of extremely last centrifugal supernatant liquid is 6.5 ~ 7.5;
The 7th step, is placed in deionized water for ultrasonic the precipitation of the 6th step gained and disperses, and after centrifugal treating, gained upper solution is graphene oxide dispersion liquid;
The 8th step adds oxalic acid powder in graphene oxide dispersion liquid, and then heating isothermal reaction under the condition stirring, reheats to remove excessive oxalic acid, obtains the graphene solution that homogeneous disperses.
In the first step, described Graphite Powder 99 is 400-600 object natural graphite powder; The mass concentration of the described vitriol oil is 68% ~ 98%; Preferably, the mass concentration of the vitriol oil is 98%.
In the first step, described supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument of ultrasonic power 120 ~ 400w and operating frequency are 20 ~ 40kHz, the alternately supersound process of the ultrasonic cell disrupte machine of ultrasonic power 800 ~ 1200w, and the total time of alternate treatment is 1 ~ 2h.
In the 3rd step, the mass concentration of described dilute sulphuric acid is 5% ~ 10%; Preferably, be 10%.
In the 3rd step, supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument supersound process of ultrasonic power 120 ~ 400w, and the time of processing is 0.5-1h.
In the 5th step, the mass concentration of described superoxol is 1 ~ 3%; Preferably, be 3%.
In the 6th step, the mass concentration of described hydrochloric acid is 5% ~ 10%; Preferably, be 10%.
In the 6th step, the temperature of deionized water is lower than 10 ℃, and the condition of centrifuge washing is: centrifuge speed: 8000 ~ 10000r/min; Centrifugation time 15 ~ 30min.
In the 7th step, described ultrasonic dispersion refers to that by operating frequency be 20 ~ 40kHz, and the ultrasonic disintegrator of ultrasonic power 800 ~ 1200w carries out supersound process; The time of supersound process is 0.5 ~ 2h.
The amount ratio of the deionized water in Graphite Powder 99, SODIUMNITRATE, the vitriol oil, potassium permanganate, dilute sulphuric acid, the 4th step, superoxol, hydrochloric acid is: 1g:(0.45-0.55) g:(23-25) ml:(2.5-3.5) g:(18-22) ml:(55-65) ml:(18-22) ml:(38-42) ml; Graphene dispersing solution in the 8th step, the amount ratio of oxalic acid are 20ml:(2.5-3.5) g.
Preferably, in the 8th step, obtain after graphene solution, then through except desolventizing, obtain graphene powder.
The present invention, by conjunction with physics and chemical process, improves intercalation and the extent of exfoliation of graphite oxide, improves the preparation efficiency of Graphene, than traditional method productive rate, improves 25% ~ 30%.
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1:
1, under ice-water bath condition, by 500 object particulate state natural graphite 1g, SODIUMNITRATE 0.5g adds in 250mL there-necked flask.Then the 24mL vitriol oil (mass concentration is 98%) is slowly added in there-necked flask and fully stir, maintenance system temperature of reaction is about 0 ℃, by operating frequency, be first 20kHz, the ultrasonic cell disrupte machine supersound process 15min of ultrasonic power 800w, then by operating frequency, be 20kHz, the ultrasonic cleaning instrument supersound process 30min of ultrasonic power 120w, by operating frequency, be finally 20kHz again, the ultrasonic cell disrupte machine supersound process 15min of ultrasonic power 800w, in supersound process process, must keep system temperature to be about 0 ℃ with ice bath, after supersound process, fully stir 2 ~ 3h.
2,3.0g potassium permanganate is added in there-necked flask, keep temperature of reaction system lower than 10 ℃, insulated and stirred 16h, preparation feedback suspension.
3, to reaction suspension, slowly add 20ml, the dilute sulphuric acid that mass concentration is 10%, is 20kHz by operating frequency, then the ultrasonic cleaning instrument supersound process 0.5h of ultrasonic power 120w under the condition stirring, fully reacts 2h.
4, add 60ml deionized water, keep system temperature of reaction lower than 10 ℃, fully react 6h.
5, keep temperature of reaction system not higher than under the condition of 10 ℃, dropwise add 20ml, the superoxol that mass concentration is 3%, until gas is overflowed completely.
6, add 40ml, the hydrochloric acid that mass concentration is 10%, fully reaction, does not use and processes higher than the deionized water repeated centrifugation of 10 ℃, until the pH of supernatant liquor is neutral.
7, the precipitation operating frequency of gained, be 20kHz, the ultrasonic disintegrator supersound process 0.5h of ultrasonic power 800w, ultrasonic being scattered in deionized water, after centrifugal treating, upper solution is graphene oxide dispersion liquid.
8, the graphene oxide solution that 20mL homogeneous is disperseed, adds 2.5g oxalic acid powder, then under the condition stirring, is added to 75 ℃ and isothermal reaction 24h, reheats to 150 ℃ to remove excessive oxalic acid, obtains the graphene solution that homogeneous disperses.
9, remove the solvent in solution, obtain graphene powder.
Fig. 1-2 is the scanning electron microscope diagram sheet of Graphene in the embodiment of the present invention 1; Fig. 3 is the transmission electron micrograph of Graphene in the embodiment of the present invention 1.
embodiment 2:
1, under ice-water bath condition, by 500 object particulate state natural graphite 1g, SODIUMNITRATE 0.5g adds in 250mL there-necked flask.Then the 24mL vitriol oil (mass concentration is 98%) is slowly added in there-necked flask and fully stir, maintenance system temperature of reaction is about 0 ℃, by operating frequency, be first 20kHz, the ultrasonic cleaning instrument supersound process 15min of ultrasonic power 120w, then by operating frequency, be 20kHz, the ultrasonic cell disrupte machine supersound process 30min of ultrasonic power 800w, by operating frequency, be finally 20kHz again, the ultrasonic cleaning instrument supersound process 15min of ultrasonic power 120w, in supersound process process, must keep system temperature to be about 0 ℃ with ice bath, after supersound process, fully stir 2 ~ 3h.
2,3.0g potassium permanganate is added in there-necked flask, keep temperature of reaction system lower than 10 ℃, insulated and stirred 16h, preparation feedback suspension.
3, to reaction suspension, slowly add 20ml, mass concentration is 10% dilute sulphuric acid, by operating frequency, is 20kHz, then the ultrasonic cleaning instrument supersound process 0.5h of ultrasonic power 120w under the condition stirring, fully reacts 2h.
4, add 60ml deionized water, keep system temperature of reaction lower than 10 ℃, fully react 6h.
5, keep temperature of reaction system not higher than under the condition of 10 ℃, dropwise add 20ml, mass concentration is 3% superoxol, until gas is overflowed completely.
6, add 40ml, mass concentration is 10% hydrochloric acid, fully reaction is not used and is processed higher than the deionized water repeated centrifugation of 10 ℃, until the pH of supernatant liquor is neutral.
7, the precipitation operating frequency of gained, be 20kHz, the ultrasonic disintegrator supersound process 0.5h of ultrasonic power 800w, ultrasonic being scattered in deionized water, after centrifugal treating, upper solution is graphene oxide dispersion liquid.
8, the graphene oxide solution that 20mL homogeneous is disperseed, adds 2.5g oxalic acid powder, then under the condition stirring, is added to 75 ℃ and isothermal reaction 24h, reheats to 150 ℃ to remove excessive oxalic acid, obtains the graphene solution that homogeneous disperses.
9, remove the solvent in solution, obtain graphene powder.
embodiment 3:
1, under ice-water bath condition, by 500 object particulate state natural graphite 1g, SODIUMNITRATE 0.5g adds in 250mL there-necked flask.Then the 24mL vitriol oil (mass concentration is 98%) is slowly added in there-necked flask and fully stir, keep system temperature of reaction not higher than 5 ℃, fully react 3h.
2,3.0g potassium permanganate is added in there-necked flask, keep temperature of reaction system in 20～30 ℃, insulated and stirred 3h.
3, add 500ml rubble ice, dropwise add 20ml, the superoxol that mass concentration is 3%, until gas is overflowed completely.
4, add 20ml, the hydrochloric acid that mass concentration is 10%, fully reaction, does not use and processes higher than the deionized water repeated centrifugation of 10 ℃, until the pH of supernatant liquor is neutral.
5, the precipitation operating frequency of gained, be 20kHz, the ultrasonic disintegrator supersound process 0.5h of ultrasonic power 800w, ultrasonic being scattered in deionized water, after centrifugal treating, upper solution is graphene oxide dispersion liquid.
6, the graphene oxide solution that 20mL homogeneous is disperseed, adds 2.5g oxalic acid powder, then under the condition stirring, is added to 75 ℃ and isothermal reaction 24h, reheats to 150 ℃ to remove excessive oxalic acid, obtains the graphene solution that homogeneous disperses.
9, remove the solvent in solution, obtain graphene powder.
In embodiment 1-3, productive rate is respectively: embodiment 1 productive rate: 11.6%; Embodiment 2 productive rates: 10.7%; Embodiment 3 productive rates: 9.1%.
As a comparison, and the present invention's employing " preparation of Graphene and chemical property thereof, Yang Changling etc., power technology, 02 phase in 2010, the method for reporting in p177-180 is carried out the synthetic of Graphene, and the productive rate that obtains Graphene is 8.3%.
Claims (10)
1. a preparation method for Graphene, is characterized in that: comprise the following steps:
The first step, under-5 ~ 0 ℃ of condition, adds Graphite Powder 99, SODIUMNITRATE in reaction vessel, then adds the vitriol oil, keeps temperature of reaction system at-5 ~ 0 ℃, and supersound process, then fully stirs;
Second step adds potassium permanganate in the first step gained solution, keeps temperature of reaction system not higher than 10 ℃, stirs 16 ~ 24h, prepares graphite suspension;
The 3rd step adds dilute sulphuric acid in graphite suspension, and then supersound process under the condition stirring, fully reacts 2 ~ 6h;
The 4th step, then add deionized water, keep temperature of reaction system not higher than 10 ℃, fully react 6 ~ 12h;
The 5th step, keeps temperature of reaction system not higher than under the condition of 10 ℃, dropwise adds superoxol, until gas is overflowed completely;
The 6th step, adds hydrochloric acid, and fully reaction, then uses reaction product deionized water centrifuge washing, and the pH of extremely last centrifugal supernatant liquid is 6.5 ~ 7.5;
The 7th step, is placed in deionized water for ultrasonic the precipitation of the 6th step gained and disperses, and after centrifugal treating, gained upper solution is graphene oxide dispersion liquid;
The 8th step adds oxalic acid powder in graphene oxide dispersion liquid, and then heating isothermal reaction under the condition stirring, reheats to remove excessive oxalic acid, obtains the graphene solution that homogeneous disperses.
2. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the first step, described Graphite Powder 99 is 400-600 object natural graphite powder; The mass concentration of the described vitriol oil is 68% ~ 98%.
3. the preparation method of a kind of Graphene according to claim 1, it is characterized in that: in the first step, described supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument of ultrasonic power 120 ~ 400w and operating frequency are 20 ~ 40kHz, the alternately supersound process of the ultrasonic cell disrupte machine of ultrasonic power 800 ~ 1200w, the total time of alternate treatment is 1 ~ 2h.
4. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 3rd step, the mass concentration of described dilute sulphuric acid is 5% ~ 10%.
5. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 3rd step, supersound process refers to that operating frequency is 20 ~ 40kHz, the ultrasonic cleaning instrument supersound process of ultrasonic power 120 ~ 400w, and the time of processing is 0.5-1h.
6. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 5th step, the mass concentration of described superoxol is 1 ~ 3%.
7. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 6th step, the mass concentration of described hydrochloric acid is 5% ~ 10%.
8. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 6th step, the temperature of deionized water is lower than 10 ℃, and the condition of centrifuge washing is: centrifuge speed: 8000 ~ 10000r/min; Centrifugation time 15 ~ 30min.
9. the preparation method of a kind of Graphene according to claim 1, is characterized in that: in the 7th step, described ultrasonic dispersion refers to that by operating frequency be 20 ~ 40kHz, and the ultrasonic disintegrator of ultrasonic power 800 ~ 1200w carries out supersound process; The time of supersound process is 0.5 ~ 2h.
10. the preparation method of a kind of Graphene according to claim 1, is characterized in that: the amount ratio of the deionized water in Graphite Powder 99, SODIUMNITRATE, the vitriol oil, potassium permanganate, dilute sulphuric acid, the 4th step, superoxol, hydrochloric acid is: 1g:(0.45-0.55) g:(23-25) ml:(2.5-3.5) g:(18-22) ml:(55-65) ml:(18-22) ml:(38-42) ml; Graphene dispersing solution in the 8th step, the amount ratio of oxalic acid are 20ml:(2.5-3.5) g.
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| CN105565309A (en) * | 2016-02-16 | 2016-05-11 | 西安天泰化玻仪器有限公司 | Method for preparing single-layer graphene |
| CN107304047B (en) * | 2016-04-21 | 2020-05-26 | 常州二维碳素科技股份有限公司 | Dispersing method of multilayer graphene |
| CN107304047A (en) * | 2016-04-21 | 2017-10-31 | 常州二维碳素科技股份有限公司 | A kind of process for dispersing of multi-layer graphene |
| WO2018036425A1 (en) * | 2016-08-22 | 2018-03-01 | 广东纳路纳米科技有限公司 | Three-dimensional graphene-based modified rubber composite material and preparation method therefor |
| CN106398800A (en) * | 2016-08-31 | 2017-02-15 | 山东金麒麟股份有限公司 | Preparation method of graphene lubricant |
| CN106986707A (en) * | 2017-05-16 | 2017-07-28 | 东北农业大学 | A kind of liquid level fertilizer and preparation method containing modified graphene oxide |
| CN107964396A (en) * | 2017-11-30 | 2018-04-27 | 陕西理工大学 | A kind of graphene photothermal conversion materiat preparation method |
| CN112661144A (en) * | 2021-01-12 | 2021-04-16 | 西北工业大学 | Method for preparing nitrogen-doped graphene ink with assistance of sodium deoxycholate |
| CN112661144B (en) * | 2021-01-12 | 2023-08-29 | 西北工业大学 | Method for preparing nitrogen-doped graphene ink with assistance of sodium deoxycholate |
| CN113247889A (en) * | 2021-06-16 | 2021-08-13 | 河南师范大学 | Method for preparing double-layer graphene |
| CN114292069A (en) * | 2022-01-06 | 2022-04-08 | 哈尔滨工业大学 | Method for efficiently preparing high-early-strength graphene oxide cement paste |
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