CN102760866A - Preparation method of nitrogen-doped graphene - Google Patents
Preparation method of nitrogen-doped graphene Download PDFInfo
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Abstract
The invention relates to a preparation method of nitrogen-doped graphene. According to the invention, urea is adopted as a reducing agent, and is subjected to a hydro-thermal reaction with graphene, such that the nitrogen-doped graphene is obtained. According to the invention, the hydro-thermal method is adopted, a relatively high temperature is not required, requirements on equipment are low, and energy can be saved. During the preparation process, urea is adopted as the reducing agent. Urea is advantaged in non-toxicity and low environment pollution. The preparation method is advantaged in simple process, short reaction time, and relatively high efficiency. With the method, the prepared nitrogen-doped graphene is advantaged in good performance.
Description
[technical field]
The present invention relates to the synthetic field of nano-carbon material, relate in particular to a kind of preparation method of nitrogen-doped graphene.
[background technology]
The strong K sea nurses of the peace moral of Univ Manchester UK (Andre K.Geim) etc. were prepared grapheme material in 2004, pay attention to widely because its particular structure and photoelectric property have received people.Mono-layer graphite has big specific area, good conduction, heat conductivility and low thermal coefficient of expansion.Especially its high conductivity matter, big specific surface character and the structural property of its monolayer two-dimensional nano yardstick can be used as electrode material in ultracapacitor and lithium ion battery.Traditional method for preparing Graphene has multiple, as: (1) micromechanics is peeled off method, and this method can only produce the extremely limited graphene film of quantity, can only be as basic research; (2) ultra high vacuum Graphene epitaxial growth method, the structural limitations of the expensive and sequin of this method its application; (3) chemical vapour deposition technique (CVD), the method can satisfy the requirement of scale preparation high-quality Graphene, but cost is higher, complex process; (4) solvent is peeled off method, and the method shortcoming is that productive rate is very low, limits its commercial application.
Doping is the method that a kind of method commonly used is used for adjusting the grapheme material characteristic electron, and theoretical and experimental study shows that Graphene band structure after nitrogen mixes can change, and compares with pure Graphene, and the range of application of nitrogen-doped graphene will be expanded greatly.But preparation method's complex process of traditional nitrogen-doped graphene, cost are higher, have limited the further application of nitrogen-doped graphene.
[summary of the invention]
Based on this, be necessary to provide that a kind of preparation technology is simple, the preparation method of lower-cost nitrogen-doped graphene.
A kind of preparation method of nitrogen-doped graphene comprises the steps:
Step 1: graphite raw material is carried out oxidation processes prepare graphite oxide;
Step 2: graphite oxide is dissolved in ultrasonic dispersion prepares the graphene oxide solution that concentration is 0.1～2mg/mL in the solvent;
Step 3: the adding mass concentration is 20～50% urea liquid in graphene oxide solution, mixes, and obtains the mixed solution of graphene oxide and urea, and wherein, the volume ratio of graphene oxide solution and urea liquid is 8～12: 1;
Step 4: the mixed solution of graphene oxide and urea is carried out hydro-thermal reaction under 80～200 ℃, promptly obtain nitrogen-doped graphene.
Preferably, in the step 1, graphite raw material is a purity more than or equal to 99.5% natural flake graphite.
Preferably, in the step 1, graphite raw material is carried out oxidation processes comprise the steps: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid; Stir, cool off more than 6 hours suction filtration; Washing is to neutral, and drying obtains biased sample;
Biased sample is added in 0 ℃ the concentrated sulfuric acid, adds potassium permanganate again, the temperature of system remains on below 20 ℃; In 35 ℃ oil bath, keep then slowly adding deionized water, after 15 minutes after 2 hours; Add the deionized water contain hydrogen peroxide solution again, become glassy yellow until the color of solution, while hot suction filtration; Using concentration again is that 10% hydrochloric acid washs, suction filtration, and 60 ℃ of vacuumizes promptly obtain graphite oxide.
Preferably, solvent is a water in the step 2, and ultrasonic jitter time is 1 hour.
Preferably, in the step 2, the concentration of graphene oxide solution is 0.5mg/mL.
Preferably, in the step 3, the mass concentration of urea liquid is 40%.
Preferably, in the step 4, the temperature of hydro-thermal reaction is 120 ℃.
Use hydro thermal method in the above-mentioned preparation process, need not use higher temperature, to equipment require low, simultaneously can energy savings; Use urea as reducing agent in the preparation process, nontoxic, environmental pollution is little.This preparation method's flow process is simple, and the reaction time is short, and efficient is higher.Nitrogen-doped graphene better performances through this method preparation.
[description of drawings]
Fig. 1 is preparation method's flow chart of the nitrogen-doped graphene of an execution mode.
Fig. 2 is applied to the constant current charge-discharge curve chart in the ultracapacitor for embodiment 1 nitrogen-doped graphene material as electrode material.
[embodiment]
Mainly combine accompanying drawing and specific embodiment that the preparation method of nitrogen-doped graphene is done further detailed explanation below.
As shown in Figure 1, the preparation method of the nitrogen-doped graphene of an execution mode comprises the steps:
Step S110: graphite raw material is carried out oxidation processes prepare graphite oxide.
Above-mentioned graphite raw material can be various form graphite powders, like crystalline flake graphite, crystalloid graphite etc.The preferred purity of this execution mode is not less than 99.5% natural flake graphite.
Wherein, graphite raw material is carried out oxidation processes prepare graphite oxide and can adopt following method: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir; Cooling is more than 6 hours, and suction filtration washs to neutral; Drying obtains biased sample;
Biased sample is added in 0 ℃ the concentrated sulfuric acid, adds potassium permanganate again, the temperature of system remains on below 20 ℃; In 35 ℃ oil bath, keep then slowly adding deionized water, after 15 minutes after 2 hours; Add the deionized water contain hydrogen peroxide solution again, become glassy yellow until the color of solution, while hot suction filtration; Using concentration again is that 10% hydrochloric acid washs, suction filtration, and 60 ℃ of vacuumizes promptly obtain graphite oxide.
Step S120: graphite oxide is dissolved in ultrasonic dispersion prepares the graphene oxide solution that concentration is 0.1～2mg/mL in the solvent.
Specifically be the graphite oxide for preparing among the step S110 to be added to the water carry out ultrasonic dispersion 1 hour, form the finely dispersed graphene oxide solution of monolithic layer, the concentration that makes graphene oxide is 0.1～2mg/mL.The concentration of the preferred graphene oxide of this execution mode is 0.5mg/mL.
Step S130: the adding mass concentration is 20～50% urea liquid in graphene oxide solution, mixes, and obtains the mixed solution of graphene oxide and urea.
The concentration of the preferred urea liquid of this execution mode is 40%.
Step S140: the mixed solution of graphene oxide and urea is carried out hydro-thermal reaction under 80～200 ℃, promptly obtain nitrogen-doped graphene.
Specifically be that the mixed solution of graphene oxide and urea is packed in the water heating kettle, under 80～200 ℃, carry out hydro-thermal reaction and promptly obtain nitrogen-doped graphene.
Urea is not only made reducing agent but also for nitrogen mixes nitrogenous source is provided under hydrothermal condition, graphene oxide carries out nitrogen simultaneously and mixes in the process of reduction, thereby nitrogen-atoms enters into Graphene lamella structure.
The preferred hydrothermal temperature of this execution mode is 120 ℃.
The percentage composition of nitrogen-atoms is 0.1～5% in the nitrogen-doped graphene that this execution mode makes.
Use hydro thermal method in the above-mentioned preparation process, need not use higher temperature, to equipment require low, simultaneously can energy savings; Use urea as reducing agent in the preparation process, nontoxic, environmental pollution is little.This preparation method's flow process is simple, and the reaction time is short, and efficient is higher.Nitrogen-doped graphene better performances through this method preparation.
Below be the specific embodiment part:
Embodiment 1
Graphite raw material → graphite oxide → graphene oxide solution → graphene oxide and urea mixed solution → nitrogen-doped graphene
(1) graphite raw material: 50 order purity are 99.5% natural flake graphite.
(2) graphite oxide: 20g graphite raw material, 10g potassium peroxydisulfate and 10g phosphorus pentoxide added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, washing is to neutral, drying, biased sample;
Dried biased sample is added in 0 ℃, the concentrated sulfuric acid of 230mL, adds 60g potassium permanganate again, the temperature of system remains on below 20 ℃, in 35 ℃ oil bath, keeps then slowly adding the 920mL deionized water after 2 hours;
After 15 minutes, in system, add the 2.8L deionized water again, become glassy yellow until the mixture color; Suction filtration while hot; Using 5L concentration again is that 10% hydrochloric acid washs, and suction filtration promptly obtained graphite oxide in 48 hours 60 ℃ of vacuumizes; Wherein, containing 50mL concentration in the above-mentioned 2.8L deionized water is 30% hydrogen peroxide solution.
(3) graphene oxide solution: with the ultrasonic dispersion 1 hour that is added to the water of the graphite oxide of preparation in the step (2), forming concentration is the homodisperse graphene oxide solution of monolithic layer of 0.5mg/mL.
(4) graphene oxide and urea mixed solution: the adding mass fraction is 40% urea liquid in the graphene oxide solution of step (3); The volume ratio of graphene oxide solution and urea liquid is 8: 1; Stirred 10 minutes; Both are mixed, obtain graphene oxide and urea mixed solution.
(5) nitrogen-doped graphene: the mixed solution of step (4) gained is packed in the water heating kettle, obtain nitrogen-doped graphene 120 ℃ of following hydro-thermal reactions.
In order to test the capacitive property of present embodiment nitrogen-doped graphene, the nitrogen-doped graphene that makes is made into electrode for capacitors, carry out charge-discharge test.Shown in specific as follows:
With nitrogen-doped graphene material by means of rolling slabbing, and use card punch to break into the circular electrode of diameter, accurately weigh as 15mm;
In glove box, this electrode, barrier film and electrolyte are assembled into ultracapacitor according to the ultracapacitor manufacture craft, its septation is celgard2000 (U.S. Nader Company products), and electrolyte is the Et of 1mol/L
4NBF
4/ AN solution.
Ultracapacitor constant current charge-discharge curve chart, as shown in Figure 2, transverse axis: time (time), unit second (S); The longitudinal axis: voltage (Voltage), unit volt (V); Wherein, the test voltage scope is 0～2.5 volt, and measuring current is 1A/g; Equipment is the blue electric CT-2001A8 in the Wuhan battery test system of filling enamel, and glove box is German Braun glove box.As can be seen from Figure 2 the charge-discharge performance of the nitrogen-doped graphene that makes of present embodiment is stable.
Embodiment 2
Step (1) and step (2) are with embodiment 1.
(3) graphene oxide solution: with the ultrasonic dispersion 1 hour that is added to the water of the graphite oxide of preparation in the step (2), forming concentration is the homodisperse graphene oxide solution of monolithic layer of 0.1mg/mL.
(4) graphene oxide and urea mixed solution: the adding mass fraction is 20% urea liquid in the graphene oxide solution of step (3); The volume ratio of graphene oxide solution and urea liquid is 10: 1; Stirred 10 minutes; Both are mixed, obtain graphene oxide and urea mixed solution.
(5) nitrogen-doped graphene: the mixed solution of step (4) gained is packed in the water heating kettle, obtain nitrogen-doped graphene 80 ℃ of following hydro-thermal reactions.
Embodiment 3
Step (1) and step (2) are with embodiment 1.
(3) graphene oxide solution: with the ultrasonic dispersion 1 hour that is added to the water of the graphite oxide of preparation in the step (2), forming concentration is the homodisperse graphene oxide solution of monolithic layer of 1mg/mL.
(4) graphene oxide and urea mixed solution: the adding mass fraction is 50% urea liquid in the graphene oxide solution of step (3); The volume ratio of graphene oxide solution and urea liquid is 12: 1; Stirred 10 minutes; Both are mixed, obtain graphene oxide and urea mixed solution.
(5) nitrogen-doped graphene: the mixed solution of step (4) gained is packed in the water heating kettle, obtain nitrogen-doped graphene 120 ℃ of following hydro-thermal reactions.
Embodiment 4
Step (1) and step (2) are with embodiment 1.
(3) graphene oxide solution: with the ultrasonic dispersion 1 hour that is added to the water of the graphite oxide of preparation in the step (2), forming concentration is the homodisperse graphene oxide solution of monolithic layer of 2mg/mL.
(4) graphene oxide and urea mixed solution: the adding mass fraction is 50% urea liquid in the graphene oxide solution of step (3); The volume ratio of graphene oxide solution and urea liquid is 10: 1; Stirred 10 minutes; Both are mixed, obtain graphene oxide and urea mixed solution.
(5) nitrogen-doped graphene: the mixed solution of step (4) gained is packed in the water heating kettle, obtain nitrogen-doped graphene 200 ℃ of following hydro-thermal reactions.
Embodiment 5
Step (1) and step (2) are with embodiment 1.
(3) graphene oxide solution: with the ultrasonic dispersion 1 hour that is added to the water of the graphite oxide of preparation in the step (2), forming concentration is the homodisperse graphene oxide solution of monolithic layer of 0.5mg/mL.
(4) graphene oxide and urea mixed solution: the adding mass fraction is 50% urea liquid in the graphene oxide solution of step (3); The volume ratio of graphene oxide solution and urea liquid is 10: 1; Stirred 10 minutes; Both are mixed, obtain graphene oxide and urea mixed solution.
(5) nitrogen-doped graphene: the mixed solution of step (4) gained is packed in the water heating kettle, obtain nitrogen-doped graphene 160 ℃ of following hydro-thermal reactions.
The above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with accompanying claims.
Claims (7)
1. the preparation method of a nitrogen-doped graphene is characterized in that, comprises the steps:
Step 1: graphite raw material is carried out oxidation processes prepare graphite oxide;
Step 2: said graphite oxide is dissolved in ultrasonic dispersion prepares the graphene oxide solution that concentration is 0.1～2mg/mL in the solvent;
Step 3: the adding mass concentration is 20～50% urea liquid in said graphene oxide solution, mixes, and obtains the mixed solution of graphene oxide and urea, and wherein, the volume ratio of graphene oxide solution and urea liquid is 8～12: 1;
Step 4: the mixed solution of said graphene oxide and urea is carried out hydro-thermal reaction under 80～200 ℃, promptly obtain said nitrogen-doped graphene.
2. the preparation method of nitrogen-doped graphene as claimed in claim 1 is characterized in that, in the step 1, said graphite raw material is a purity more than or equal to 99.5% natural flake graphite.
3. according to claim 1 or claim 2 the preparation method of nitrogen-doped graphene is characterized in that, in the step 1; Said graphite raw material is carried out oxidation processes comprise the steps: said graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours; Suction filtration; Washing is to neutral, and drying obtains biased sample;
Said biased sample is added in 0 ℃ the concentrated sulfuric acid, adds potassium permanganate again, the temperature of system remains on below 20 ℃; In 35 ℃ oil bath, keep then slowly adding deionized water, after 15 minutes after 2 hours; Add the deionized water contain hydrogen peroxide solution again, become glassy yellow until the color of solution, while hot suction filtration; Using concentration again is that 10% hydrochloric acid washs, suction filtration, and 60 ℃ of vacuumizes promptly obtain graphite oxide.
4. the preparation method of nitrogen-doped graphene as claimed in claim 1 is characterized in that, solvent described in the step 2 is a water, and ultrasonic jitter time is 1 hour.
5. the preparation method of nitrogen-doped graphene as claimed in claim 1 is characterized in that, in the step 2, the concentration of said graphene oxide solution is 0.5mg/mL.
6. the preparation method of nitrogen-doped graphene as claimed in claim 1 is characterized in that, in the step 3, the mass concentration of said urea liquid is 40%.
7. the preparation method of nitrogen-doped graphene as claimed in claim 1 is characterized in that, in the step 4, the temperature of hydro-thermal reaction is 120 ℃.
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| CN107622879A (en) * | 2017-10-24 | 2018-01-23 | 福建宸琦新材料科技有限公司 | The preparation method of nitrogen-doped graphene/carbon nanotube aerogel electrode |
| CN107622879B (en) * | 2017-10-24 | 2020-01-10 | 福建宸琦新材料科技有限公司 | Preparation method of nitrogen-doped graphene/carbon nanotube aerogel electrode |
| CN107857253A (en) * | 2017-12-04 | 2018-03-30 | 内蒙古科技大学 | A kind of three-dimensional porous graphene of N doping and preparation method thereof |
| CN109336094A (en) * | 2018-12-07 | 2019-02-15 | 成都理工大学 | A kind of nitrogen-doped graphene and preparation method |
| CN109336094B (en) * | 2018-12-07 | 2022-02-01 | 成都理工大学 | Nitrogen-doped graphene and preparation method thereof |
| CN109650999A (en) * | 2019-02-12 | 2019-04-19 | 东北农业大学 | A kind of preparation method and application of graphene waste material embedding urea |
| CN109650999B (en) * | 2019-02-12 | 2022-03-08 | 东北农业大学 | Preparation method and application of graphene waste embedded urea |
| CN114573099A (en) * | 2022-03-02 | 2022-06-03 | 齐鲁工业大学 | Method for promoting enrichment of anaerobic ammonium oxidation bacteria by nitrogen-doped graphene |
| CN118324134A (en) * | 2024-06-13 | 2024-07-12 | 深圳市犇越科技有限公司 | Graphene lithium battery composite material and preparation method thereof |
| CN118324134B (en) * | 2024-06-13 | 2024-09-20 | 于忠军 | Graphene lithium battery composite material and preparation method thereof |
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