CN102887498B - Preparation method of nitrogen-doped graphene - Google Patents
Preparation method of nitrogen-doped graphene Download PDFInfo
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Abstract
The invention provides a preparation method of nitrogen-doped graphene by a chemical vapor deposition method, which comprises the following steps of: providing a substrate with high temperature resistance, and a solid and/or liquid organic carbon source compound; preparing the organic carbon source compound into solution or suspension; coating the solution or suspension of the organic carbon source compound on the surface of the substrate; heating the substrate coated by solution or suspension containing the organic carbon source compound to 500-1300 DEG C under an oxygen-free and vacuum environment, then leading into gaseous nitrogen compound to react to obtain nitrogen-doped graphene. The preparation method of nitrogen-doped graphene provided by the invention prepares the solid and/or liquid organic carbon source compound into solution or suspension and coats directly on the surface of the substrate to make the organic carbon source compound react with the introduced nitrogen compound. The method provided by the invention has the advantages of having no need of adding a catalyst, simplifying the production process of nitrogen-doped graphene effectively and reducing the production cost. At the same time, the nitrogen-doped graphene prepared by the chemical vapor deposition method enables the doped graphene to be controlled easily in the amount, to be doped uniformly and to be high in electrochemical stability.
Description
Technical field
The invention belongs to the technical field of carbon material, be specifically related to a kind of preparation method of nitrating Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), is the carbon material as thin as a wafer of single or multiple lift.Because its unique structure and photoelectric property become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, many scientific workers are attracted.Single-layer graphene has large specific surface area, and good conduction, heat conductivility and low thermal expansivity, can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.The method of preparing at present Graphene mainly contains graphite breakaway, chemistry redox method, ultrasonic stripping method etc.But, prepare on a large scale in the process of Graphene by redox method at present, reduction Graphene later also contain small amount-OH ,-C-O-C-and-oxygen-containing functional groups such as COOH, these functional groups can reduce electrochemical stability and the electrochemical stability of Graphene.
At present, there is adopting the correlative study of process for preparing graphenes by chemical vapour deposition, still, existing chemical Vapor deposition process need to utilize catalyzer, and this catalyzer is that metal or metallic compound make catalyzer, but when this catalyzer is placed on substrate, can cause catalyst distribution inhomogeneous.In order to solve the problem of this catalyst distribution inequality, existing general using chemical Vapor deposition process, physical vaporous deposition, vacuum thermal evaporation method, magnetron sputtering method, plasma enhanced chemical vapor deposition method and print process to substrate, increase the homogeneity of above-mentioned catalyst distribution by catalyst deposit.Therefore, existing employing process for preparing graphenes by chemical vapour deposition needs to add in addition catalyzer, and high to equipment requirements, and complicated operation, causes high cost.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide that a kind of technique is simple, productive rate is high, production cost is low, the preparation method of the nitrating Graphene being easy to operate and control.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
A preparation method for nitrating Graphene, comprises the steps:
Substrate, solid-state and/or liquid organic carbon source compound are provided;
Described organic carbon source compound is mixed with to solution or suspension liquid;
Described solution or suspension liquid containing organic carbon-source cpd is coated in to described substrate surface;
Under oxygen-free environment, vacuum condition, described being coated with containing the solution of organic carbon-source cpd or the substrate of suspension liquid is warming up to 500～1300 DEG C, then the nitrogen source compound that passes into gaseous state reacts, obtain described nitrating Graphene.
Solid-state and/or liquid organic carbon source compound is mixed with solution or suspension liquid by the preparation method of above-mentioned nitrating Graphene, and be directly coated in the surface of substrate, the gaseous nitrogen source compound direct reaction that makes organic carbon source compound and pass into, do not need to add in addition catalyzer, effectively simplify the production technique of nitrating Graphene, reduce production cost, simultaneously, adopt the synthetic nitrating Graphene of chemical Vapor deposition process, make in nitrating Graphene that itrogen content of getter with nitrogen doped is easy to control, uniform doping, electrochemical stability performance is high.
Brief description of the drawings
Fig. 1 is preparation method's process flow diagram of embodiment of the present invention nitrating Graphene;
Fig. 2 is the Electronic Speculum figure of the nitrating Graphene prepared of the embodiment of the present invention 1;
Fig. 3 is the X ray electronic spectrum of the nitrating Graphene prepared of the embodiment of the present invention 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides that a kind of technique is simple, productive rate is high, production cost, the preparation method of the nitrating Graphene being easy to operate and control.The preparation method's of this nitrating Graphene technical process as shown in Figure 1, adopts chemical gaseous phase depositing process to prepare nitrating Graphene, and it comprises the steps:
S1: substrate, solid-state and/or liquid organic carbon source compound are provided;
S2: this organic carbon source compound is mixed with to solution or suspension liquid;
S3: this solution or suspension liquid containing organic carbon-source cpd is coated in to substrate surface;
S4: under oxygen-free environment, vacuum condition, this is coated with containing the solution of organic carbon-source cpd or the substrate of suspension liquid and is warming up to 500～1300 DEG C, then the nitrogen source compound that passes into gaseous state reacts, obtain described nitrating Graphene.
Particularly, in preparation method's step S1 of above-mentioned nitrating Graphene, substrate should be high temperature resistant, and as the high temperature of 500～1300 DEG C in step S4, it is preferably one or more arbitrary combination in Copper Foil, iron foil, nickel foil.The substrate of this preferred material is high temperature resistant, and thermal stability is good.
Above-mentioned organic carbon source compound is preferably at least one in ferrocene, dicyclopentadienylcobalt, nickelocene, two luxuriant manganese.This preferred organic carbon source compound has good solubility energy, can be mixed with uniform solution, and can be coated in uniformly the surface of substrate, forms even and thin rete, thereby effectively reduces the thickness of the nitrating Graphene of surviving in following step S4.In addition, in this preferred organic carbon source compound, contain metal ion, the existence of this metal ion, is conducive to the generation of nitrating Graphene, to improve the productive rate of nitrating Graphene.Certain above-mentioned organic carbon source compound also can substitute with other solid-state and/or liquid organic carbon source compounds.In the time of organic carbon source compound that selected organic carbon source compound is non-dissolubility, can be ground (as ball milling) and be prepared uniform suspension liquid.
In preparation method's step S2 of above-mentioned nitrating Graphene, for organic carbon source compound being evenly coated on substrate, this organic carbon source compound should be mixed with to mass percentage concentration and be preferably 5～30% solution or suspension liquid.
In preparation method's step S3 of above-mentioned nitrating Graphene, the method that organic carbon source compound solution is coated to substrate surface preferably adopts one or more arbitrary combination in spread coating, spin-coating method, infusion method, simplify thereby reach the production technique that this prepares nitrating Graphene method, reduced the object of production cost.
In this step S3, before substrate surface application of mixture solution, preferably in advance this substrate is cleaned, the mode of cleaning is preferably and adopts successively ionized water, ethanol, acetone ultrasonic cleaning post-drying, stand-by.Clean this substrate to remove the foreign material that stick to substrate surface, reach the object of clean substrate, to be conducive to the coating of mixture solution or suspension liquid.This substrate clean early stage referring to the purging method in the step S11 in following embodiment 1.
In preparation method's step S4 of above-mentioned nitrating Graphene, this oxygen free condition is in order to remove oxygen, and nitrating Graphene is produced can carry out smoothly, prevents that, under hot conditions, the Graphene of generation is oxidized.This oxygen free condition is the oxygen-free atmosphere that rare gas element forms, as, nitrogen atmosphere, argon gas atmosphere etc., preferably oxygen free condition is nitrogen atmosphere; Oxygen free condition can be also the condition vacuumizing, and the condition of this vacuum can not only effectively be removed oxygen, and can also remove impurity such as flying away aerial dust simultaneously, thereby further ensures the purity of nitrating Graphene.In addition, the condition of this vacuum can also promote the reaction of above-mentioned organic carbon source compound and nitrogen source compound, thereby improves the productive rate of nitrating Graphene.Wherein, the condition optimization of this vacuum is that vacuum tightness is less than 10
-3the vacuum condition of Pa.Certainly, at oxygen free condition can be the oxygen free condition of normal pressure.
In this step S4, this organic carbon source compound passing into is preferably 2～20: 1 with the carbon and nitrogen atoms ratio of the nitrogen source compound that passes into gaseous state, and the time that this organic carbon source compound and the nitrogen source compound passing into react is preferably 1～300 minute.The preferred proportion of this organic carbon source compound and nitrogen source compound consumption, in the nitrating Graphene that can make to generate, the content of nitrogen element is at a best content range, thereby further improve the electrochemical stability performance of this nitrating Graphene, make organic carbon source compound and nitrogen source compound fully react simultaneously, improve the utilization ratio of reactant, thereby further reduce production costs.The preferred time that this organic carbon source compound and nitrogen source compound react can ensure that both fully react, and the nitrating Graphene generating is fully deposited.Wherein, the gaseous nitrogen source compound passing into is preferably at least one in ammonia, nitrogen, methylamine, and this gaseous nitrogen source compound can be also the nitrogen source compound after other are vaporized certainly.
In this step S4, one or more the method for combination that provides preferred employing hot-wire chemical gas-phase deposition, radio-frequency plasma to strengthen in chemical vapour deposition, microwave plasma enhanced chemical vapour deposition, laser chemical vapor deposition, low-pressure chemical vapor deposition, aumospheric pressure cvd of the lifting of underlayer temperature and this organic carbon source compound, nitrogen source compound temperature of reaction provides thermal source.According to the difference of aforementioned thermal source presentation mode, therefore, embodiment of the present invention chemical Vapor deposition process is also preferably accordingly hot-wire chemical gas-phase deposition, radio-frequency plasma and strengthens one or more the combination in chemical vapour deposition, microwave plasma enhanced chemical vapour deposition, laser chemical vapor deposition, low-pressure chemical vapor deposition, aumospheric pressure cvd.As while adopting laser chemical vapor deposition method to provide thermal source to adopt the synthetic nitrating Graphene of laser chemical vapor deposition method, because laser energy is concentrated, can make organic carbon source compound and nitrogen source compound reaction efficiency further improve, thereby improve the production efficiency of nitrating Graphene.
In this step S4, after the reaction of organic carbon source compound and nitrogen source compound finishes, stop the heating to substrate, ensureing, under the condition of anaerobic, to make reaction system cooling.
Further, in a preferably embodiment of the present invention, the preparation method of above-mentioned nitrating Graphene also comprises the step of the purifying of nitrating Graphene synthetic in step S4.The step of this nitrating Graphene purifying is preferably: cooled substrate is put into dilute acid soln and soak 0.1～24 hour, remove the reactant that does not participate in reaction completely, by product and other impurity of production, then clean with deionized water, then dry.Wherein, the kind of diluted acid can but be not only at least one in hydrochloric acid, sulfuric acid, nitric acid.The concentration of this diluted acid is preferably more than 0.01mol/L, is less than 1mol/L.
From the above mentioned, solid-state and/or liquid organic carbon source compound is mixed with solution or suspension liquid by the preparation method of above-mentioned nitrating Graphene, and be directly coated in the surface of substrate, the gaseous nitrogen source compound direct reaction that makes organic carbon source compound and pass into, do not need to add in addition catalyzer, effectively improve the production technique of having simplified nitrating Graphene, reduce production cost, simultaneously, adopt the synthetic nitrating Graphene of chemical Vapor deposition process, make in nitrating Graphene that itrogen content of getter with nitrogen doped is easy to control, uniform doping, electrochemical stability performance is high.Wherein, by controlling the consumption of organic carbon source compound and nitrogenous source chemical combination, make the content of nitrogen element in synthetic nitrating Graphene at a best content range, thereby further improve the electrochemical stability performance of this nitrating Graphene.
Now, taking the preparation method of concrete nitrating Graphene as example, the present invention is further elaborated.
Embodiment 1:
The preparation method of nitrating Graphene, comprises the steps:
S11. by nickel foil deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate, ferrocene is mixed with to the solution that mass percentage concentration is 20wt%, is then spun on substrate surface;
S12. the substrate that is coated with ferrocene is put into reaction chamber, and enclosed reaction chamber, adopting mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep after 10 minutes, closure molecule pump, starts heating;
S13. in the time that underlayer temperature reaches 500 DEG C, keep temperature-resistant, then pass into the nitrogenous substances ammonia that flow is 10sccm, start to generate nitrating Graphene; The amount of the nitrogen wherein, passing into and ferrocene with magnitude relation: carbon and nitrogen atoms mol ratio is 10: 1;
S14. question response, after 300 minutes, stops substrate heating, and is cooled to room temperature, obtains nitrating Graphene;
S15. by surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 0.1 hour of 0.7mol/L, remove reactant, ferrous metal particle and other impurity for participating in reaction completely, then clean with deionized water, dry, collect this nitrating Graphene.
Nitrating Graphene synthetic the present embodiment 1 is carried out to Electronic Speculum (SEM) scanning analysis, and Electronic Speculum (SEM) scanned picture of this nitrating Graphene as shown in Figure 2.As shown in Figure 2, the synthetic nitrating Graphene of the present embodiment 1 is two-dimensional film shape, and its size is 0.5～5 μ m.
Nitrating Graphene synthetic the present embodiment 1 is carried out to X ray electronic spectrum (XPS) analysis, and its XPS result as shown in Figure 3.Known according to the result of Fig. 3, the synthetic nitrating Graphene nitrogen content of the present embodiment 1 is about 3.7%.
Embodiment 2
The preparation method of nitrating Graphene, comprises the steps:
S21. by Copper Foil deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate, nickelocene is mixed with to the solution that mass percentage concentration is 5wt%, is then spun on substrate surface;
S22. the substrate that is coated with nickelocene is put into reaction chamber, and enclosed reaction chamber, adopting mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep after 30 minutes, closure molecule pump, starts heating;
S23. in the time that underlayer temperature reaches 1300 DEG C, keep temperature-resistant, then pass into the nitrogenous substances methylamine that flow is 200sccm, start to generate nitrating Graphene; Wherein, pass into the amount of methylamine and nickelocene with magnitude relation: carbon and nitrogen atoms mol ratio is 2: 1;
S24. question response, after 1 minute, stops substrate heating, and is cooled to room temperature, obtains nitrating Graphene;
S25. by surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 8 hours of 0.4mol/L, remove reactant, nickel metallic particles and other impurity for participating in reaction completely, then clean with deionized water, dry, collect this nitrating Graphene.
Embodiment 3
The preparation method of nitrating Graphene, comprises the steps:
S31. by iron foil deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate, dicyclopentadienylcobalt is mixed with to the solution that mass percentage concentration is 30wt%, then blade coating is in substrate surface;
S32. the substrate that is coated with dicyclopentadienylcobalt is put into reaction chamber, and enclosed reaction chamber, adopting mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep after 1 minute, closure molecule pump, starts heating;
S33. in the time that underlayer temperature reaches 1000 DEG C, keep temperature-resistant, then to pass into flow be 100sccm nitrogenous substances ammonia, start to generate nitrating Graphene; Wherein, pass into the amount of ammonia and dicyclopentadienylcobalt with magnitude relation: carbon and nitrogen atoms mol ratio is 20: 1;
S34. question response, after 100 minutes, stops substrate heating, and is cooled to room temperature, obtains nitrating Graphene;
S35. by surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 16 hours of 0.2mol/L, remove reactant, cobalt metallic particles and other impurity for participating in reaction completely, then clean with deionized water, dry, collect this nitrating Graphene.
Embodiment 4
The preparation method of nitrating Graphene, comprises the steps:
S41. by iron foil deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate, two luxuriant manganese are mixed with to the solution that mass percentage concentration is 10wt%, are then spun on substrate surface;
S42. the substrate that is coated with mixing solutions is put into reaction chamber, and enclosed reaction chamber, adopting mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep after 20 minutes, closure molecule pump, starts heating;
S43. in the time that underlayer temperature reaches 700 DEG C, keep temperature-resistant, then pass into the nitrogenous substances nitrogen that flow is 50sccm, start to generate nitrating Graphene; The amount of the nitrogen material wherein, passing into and two luxuriant manganese with magnitude relation: carbon and nitrogen atoms mol ratio is 15: 1;
S44. question response, after 200 minutes, stops substrate heating, and is cooled to room temperature, obtains nitrating Graphene;
S45. by surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 24 hours of 0.08mol/L, remove reactant, manganese metallic particles and other impurity for participating in reaction completely, then clean with deionized water, dry, collect this nitrating Graphene.
Embodiment 5
The preparation method of nitrating Graphene, comprises the steps:
S51. by iron foil deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate, the mixture of the two luxuriant manganese that are 1: 1 by mol ratio and ferrocene is mixed with the solution that mass percentage concentration is 15wt%, is then spun on substrate surface;
S52. the substrate that is coated with mixing solutions is put into reaction chamber, and enclosed reaction chamber, adopting mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep after 20 minutes, closure molecule pump, starts heating;
S53. in the time that underlayer temperature reaches 800 DEG C, keep temperature-resistant, then pass into the mixed gas that flow is 50sccm nitrogenous substances nitrogen and ammonia, start to generate nitrating Graphene; Wherein, pass into the amount of mixed gas of nitrogen and ammonia and two luxuriant manganese and ferrocene mixture with magnitude relation: carbon and nitrogen atoms mol ratio is 12: 1;
S54. question response, after 200 minutes, stops substrate heating, and is cooled to room temperature, obtains nitrating Graphene;
S55. by surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 24 hours of 0.08mol/L, remove reactant, manganese metallic particles and other impurity for participating in reaction completely, then clean with deionized water, dry, collect this nitrating Graphene.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a preparation method for nitrating Graphene, comprises the steps:
Substrate, solid-state and/or liquid organic carbon source compound are provided;
Described organic carbon source compound is mixed with to solution or suspension liquid; Described organic carbon source compound is at least one in ferrocene, dicyclopentadienylcobalt, nickelocene, two luxuriant manganese;
Described solution or suspension liquid containing organic carbon-source cpd is coated in to described substrate surface;
Under oxygen-free environment, vacuum condition, described being coated with containing the solution of organic carbon-source cpd or the substrate of suspension liquid is warming up to 500～1300 DEG C, then the nitrogen source compound that passes into gaseous state reacts, obtain described nitrating Graphene;
In the preparation method of described nitrating Graphene, do not add catalyzer.
2. the preparation method of nitrating Graphene according to claim 1, is characterized in that: the carbon and nitrogen atoms mol ratio of described organic carbon source compound and nitrogen source compound is 2～20:1.
3. the preparation method of nitrating Graphene according to claim 1, is characterized in that: the flow that described nitrogen source compound passes into is 10～200sccm.
4. the preparation method of nitrating Graphene according to claim 1, is characterized in that: the mass percentage concentration of described solution or suspension liquid is 5～30%.
5. according to the method for the arbitrary described one-step synthesis nitrating Graphene of claim 1～4, it is characterized in that: described nitrogen source compound is at least one in nitrogen, ammonia, methylamine.
6. the preparation method of nitrating Graphene according to claim 1, is characterized in that: under described oxygen free condition for vacuum tightness is less than 10
-3the vacuum condition of Pa.
7. the preparation method of nitrating Graphene according to claim 1, is characterized in that: described substrate is at least one in Copper Foil, iron foil, nickel foil.
8. the preparation method of nitrating Graphene according to claim 1, is characterized in that: also comprise the step of described nitrating Graphene being carried out to purifying.
9. the preparation method of nitrating Graphene according to claim 8, is characterized in that: the step that described nitrating Graphene carries out purifying is greater than 0.01mol/L for nitrating Graphene is put into concentration, is less than in 1mol/L dilute acid soln and soaks 0.1～24 hour.
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| CN104058389B (en) * | 2013-03-18 | 2016-04-06 | 海洋王照明科技股份有限公司 | Boron doped graphene and preparation method thereof |
| EP2857550A1 (en) | 2013-10-02 | 2015-04-08 | Basf Se | Amine precursors for depositing graphene |
| CN104556014B (en) * | 2015-01-08 | 2017-03-29 | 复旦大学 | A kind of method of nonmetallic surface low temperature preparation doped graphene |
| CN105140455A (en) * | 2015-06-29 | 2015-12-09 | 柳州蚊敌香业有限公司 | Lithium battery module for electric vehicle |
| CN108117057B (en) * | 2016-11-30 | 2019-11-22 | 比亚迪股份有限公司 | A kind of nitrogen-doped graphene aggregation and its preparation method and application |
| CN111139453B (en) * | 2020-01-20 | 2022-11-15 | 中国科学院电工研究所 | Preparation method of high-conductivity copper/graphene composite material |
| CN112853144A (en) * | 2020-12-31 | 2021-05-28 | 杭州电子科技大学 | Preparation method of diamond/graphene/metal composite material |
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