CN103626158B - The preparation method of nitrogen-doped graphene and application thereof - Google Patents
The preparation method of nitrogen-doped graphene and application thereof Download PDFInfo
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Abstract
The invention provides a kind of preparation method of nitrogen-doped graphene and the application in ultracapacitor thereof, the preparation method of nitrogen-doped graphene is specially: carbon material and the compound containing active nitrogen element are placed in encloses container, be heated to 100 ~ 300 DEG C, obtain nitrogen-doped graphene.Prepare in the process of nitrogen-doped graphene, in a heated condition, the nitrogen-doping in the compound containing active nitrogen element is entered in carbon material, thus obtains nitrogen-doped graphene.The present invention adopts aforesaid method to prepare nitrogen-doped graphene, avoids the temperature of reaction that employing is higher, and preparation condition is gentle and production cost is lower.Azepine Graphene the present invention prepared is applied to the electrode materials of ultracapacitor, and during current density 5A/g, the specific storage of ultracapacitor can reach 190F/g; Circulate 10000 times, capability retention is 96.3%.
Description
Technical field
The present invention relates to technical field of graphene, particularly relate to preparation method and the application thereof of nitrogen-doped graphene.
Background technology
Graphene is made up of carbon six-ring, there is two-dimension periodic honeycomb lattice structure, the two-dirnentional structure of this uniqueness, make it have the physics-chem characteristic of the various excellences such as high intensity, good electroconductibility and fabulous light transmission, therefore the field such as Graphene ballistic transistor on the scene, ultracapacitor, lithium ion battery has important using value.
Doping is a kind of common method of adjustment semiconductor material Electronic Performance, and research shows, Graphene energy band structure after doping adjusts, thus makes the range of application of Graphene have great expansion, and performance also improves accordingly.Such as: using the electrode materials of the Graphene after doping as ultracapacitor, not only electroconductibility increases, and heteroatomic mixing also can produce fake capacitance, improves the specific storage of electrical condenser further.Therefore the doping of Graphene has become the focus that the numerous disciplinary study person of physics, chemistry and materialogy pays close attention to.
2009, the Liu Yun boundary seminar reported first preparation method of nitrogen-doped graphene.Author adopts chemical Vapor deposition process, and using ammonia as nitrogenous source, methane, as carbon source, is incubated 10min at 800 DEG C, has prepared which floor nitrogen-doped graphene of minority.At present, existing doped graphene mainly N doping, such as, be raw material with graphene oxide, take ammonia as nitrogenous source, carry out high temperature annealing and obtain nitrogen-doped graphene, this method prepares the higher temperature of nitrogen-doped graphene needs, makes the popularization of nitrogen-doped graphene bring limitation.
Due to the preparation method of prior art nitrogen-doped graphene, need higher Heating temperature, its preparation condition is harsh, and the preparation of nitrogen-doped graphene is limited by very large.
Summary of the invention
The technical problem that the present invention solves is the preparation method providing a kind of nitrogen-doped graphene, the method mild condition, and cost is lower.
In view of this, the invention provides a kind of preparation method of nitrogen-doped graphene, comprising:
Carbon material and the compound containing active nitrogen element are placed in encloses container, be heated to 100 ~ 300 DEG C, obtain nitrogen-doped graphene after reaction, the described compound containing active nitrogen element is gas and/or solid, and described carbon material is Graphene or graphene oxide.
Preferably, the preparation method of described graphene oxide is:
Be the ultrasonic 0.5 ~ 2h of graphene oxide colloid of 1mg/ml ~ 15mg/ml by concentration, lyophilize, obtains graphene oxide.
Preferably, also activator is comprised in described encloses container.
Preferably, described activator is water vapour, carbonic acid gas, zinc chloride, potassium hydroxide or phosphoric acid.
Preferably, the mass ratio of described carbon material and described activator is 0.1:1 ~ 10:1.
Preferably, the described compound containing active nitrogen element is one or more of nitrogen protoxide, nitrogen peroxide, volatile salt, bicarbonate of ammonia, primary ammonium phosphate, urea, trimeric cyanamide and Silver Nitrate.
Preferably, protective gas is full of in described encloses container.
Preferably, the time of described reaction is 0.5 ~ 30h.
Preferably, the mass ratio of described Graphene or graphene oxide and the described compound containing active nitrogen element is 0.1:1 ~ 50:1.
The application of nitrogen-doped graphene described in such scheme in the electrode materials preparing ultracapacitor.
The invention provides a kind of preparation method of nitrogen-doped graphene, be specially: carbon material and the compound containing active nitrogen element are placed in encloses container, are heated to 100 ~ 300 DEG C, after reaction, obtain nitrogen-doped graphene.In the process preparing nitrogen-doped graphene, in a heated condition, the nitrogen-doping in the compound containing active nitrogen element is entered in carbon material, thus obtains nitrogen-doped graphene.Compound containing active nitrogen element reacts with carbon material by the present invention in airtight environment, adds the pressure of encloses container, is conducive to promoting that active nitrogen element adulterates, thus nitrogen element just can be adulterated at a lower temperature.The present invention adopts aforesaid method to prepare nitrogen-doped graphene, avoids the temperature of reaction that employing is higher, thus makes preparation condition gentle and production cost is lower.Azepine Graphene the present invention prepared is applied to the electrode materials of ultracapacitor, and experimental result shows, during current density 5A/g, the specific storage of ultracapacitor can reach 190F/g; Circulate 10000 times, capability retention is 96.3%.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of nitrogen-doped graphene;
Fig. 2 is the TEM selected area electron diffraction figure of nitrogen-doped graphene;
Fig. 3 is x-ray photoelectron power spectrum (XPS) figure of nitrogen-doped graphene under the differential responses time;
Fig. 4 is the XPS swarming spectrogram of N (1s) in nitrogen-doped graphene;
Fig. 5 is the cyclic curve figure of nitrogen-doped graphene electrode materials under current density 5A/g condition.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method of nitrogen-doped graphene, concrete steps are:
Carbon material and the compound containing active nitrogen element are placed in encloses container, be heated to 100 ~ 300 DEG C, obtain nitrogen-doped graphene after reaction, the described compound containing active nitrogen element is gas and/or solid, and described carbon material is Graphene or graphene oxide.
According to the present invention, prepare in the process of nitrogen-doped graphene above-mentioned, described graphene oxide is specifically prepared as follows:
Be the graphene oxide colloid of 1mg/ml ~ 15mg/ml by concentration, after ultrasonic 0.5 ~ 2h, lyophilize, namely obtains graphene oxide.In order to ensure the more evenly tiny of graphene oxide fragmentation, the concentration of described graphene oxide is preferably 5 ~ 10mg/ml, and the described ultrasonic time is preferably 1 ~ 1.5h.Above-mentioned cryodesiccated principle is: after thing quick freezing to be dried, then is water vapour and the drying means that removes by ice distillation wherein in high vacuum conditions.The present invention, by after graphene oxide sonic oscillation, carries out lyophilize, by water removing wherein, and effectively ensure that the activity of graphene oxide, obtains graphene oxide.Described containing the compound of active nitrogen element and the contact area of described carbon material in order to increase, farthest reduce the temperature of reaction required for N doping, preferably, by described carbon material and the described compound containing active nitrogen element evenly after, carry out lyophilize again, after obtaining powder, then be placed in encloses container and react.It is standby that graphene oxide colloid of the present invention is preferably Hummers legal system, and Graphene colloid is preferably Ningbo Mo Xi Science and Technology Ltd..
The described compound containing active nitrogen element is gas and/or solid, is preferably nitrogen protoxide, nitrogen peroxide, volatile salt, bicarbonate of ammonia, primary ammonium phosphate, urea and trimeric cyanamide one or more.The above-mentioned gas containing active nitrogen element is placed in encloses container and produces pressure, the pressure of encloses container can be increased, thus reduce the energy of reaction, the active nitrogen wherein contained is made to be easy to be entrained in Graphene, and above-mentioned primary ammonium phosphate, urea and trimeric cyanamide are in a heated condition, decomposite ammonia, thus N doping is carried out in Graphene, in addition containing the volatile salt in the solid of active nitrogen element in a heated condition, split the carbon dioxide off and ammonia, carbonic acid gas has activation to graphene material or graphene oxide, increase the reactive behavior of carbon material, N doping is made to be easy to carry out, carbonic acid gas and ammonia add the pressure of encloses container simultaneously, more easily carry out N doping, thus N doping is carried out at a lower temperature.Same for the bicarbonate of ammonia containing active nitrogen element, in a heated condition, split the carbon dioxide off, water vapour and ammonia, carbonic acid gas and water vapour have activation to graphene material or graphene oxide, substantially increase the reactive behavior of carbon material, make N doping be easy to carry out, carbonic acid gas, water vapour and ammonia add the pressure of encloses container simultaneously, more easily carry out N doping, thus N doping is carried out at a lower temperature.According to the present invention, the described compound containing active nitrogen element is more preferably bicarbonate of ammonia or volatile salt.
In order to reduce the energy of reaction needed, N doping is reacted and is easy to carry out, the present invention also comprises activator in the process of carrying out N doping.Described activator is preferably as water vapour, carbonic acid gas, zinc chloride, potassium hydroxide or phosphoric acid, water vapour wherein or carbonic acid gas have activation to the carbon in graphene oxide or Graphene, the reactive behavior of carbon can be improved, thus energy required when reducing nitrogen-doping; Simultaneously in encloses container, described carbonic acid gas or water vapour also can increase the pressure of encloses container, and reaction is more easily carried out, thus make nitrogen be easy to be doped in Graphene.And for described zinc chloride, potassium hydroxide or phosphoric acid, it mainly plays activation, the reactive behavior of carbon can be increased, thus reactive behavior when reducing nitrogen-doping.According to the present invention, described activator is preferably carbonic acid gas or water vapour.
The present invention is described containing the compound of active nitrogen element and the mass ratio of described carbon material by regulating, and reach the object controlling nitrogen content in nitrogen-doped graphene, the mass ratio of described carbon material and described ammonium salt is preferably 1:30 ~ 10:1, is more preferably 1:5 ~ 2:1.
The present invention is preferably full of protective gas in encloses container; raw material being placed in protective atmosphere is to prevent carbon material oxidized; described protective atmosphere is preferably rare gas element or nitrogen; described protective atmosphere is more preferably argon gas or nitrogen, and described protective atmosphere most preferably is argon gas or the nitrogen that purity is more than or equal to 99%.Described encloses container is preferably withstand voltage encloses container, because the solid containing active nitrogen element may decomposite ammonia, water or other gas in a heated condition, above-mentioned gas can produce pressure in encloses container, therefore described encloses container needs to bear certain pressure, certainly the pressure born needed for is not high pressure, in order to reduce costs, the maximum pressure that bears of described encloses container is preferably 2 ~ 3MPa.The temperature of described heating is 100 ~ 300 DEG C, and be preferably 150 ~ 250 DEG C, the time of described heating is preferably 0.5 ~ 30h, is more preferably 5 ~ 20h.If Heating temperature is too low or heat-up time is too short, then the nitrogen content in nitrogen-doped graphene is then very few, thus affects the performance of nitrogen-doped graphene.
In the process preparing nitrogen-doped graphene, preferably, first described activator, carbon material and the compound containing active nitrogen element are placed in reactor by the present invention, pass into purity and be not less than the argon gas of 99% to remove the oxygen in reactor, thus avoid raw material oxidized, encloses container subsequently; Again encloses container is preferably placed in air dry oven or retort furnace is heated to 100 ~ 300 DEG C, reacts, after reaction terminates, cooling, namely obtains nitrogen-doped graphene.
The present invention with carbon material with containing the compound of active element for raw material, above-mentioned raw materials is heated to 100 ~ 300 DEG C, make a large amount of functional groups of surface of graphene oxide, as functional group's decomposition-reductions such as carboxyl, epoxy group(ing), hydroxyls, gas simultaneously containing active nitrogen element and/or solid decompose, and produce nitrogen element, in a heated condition, nitrogen enters in Graphene and N doping occurs, thus obtains nitrogen-doped graphene.In the process preparing nitrogen-doped graphene, by regulating the temperature of heating, the mass ratio of time and raw material, thus reach the object controlling N doping amount.
Nitrogen-doped graphene the present invention prepared is applied to the electrode materials preparing ultracapacitor, effectively can improve capacity and the capacity stability of ultracapacitor.The present invention is for being well known to those skilled in the art by nitrogen-doped graphene for the preparation of the method for the electrode materials of ultracapacitor, and the present invention has no particular limits.Experimental result shows, azepine Graphene prepared by the present invention is applied to the electrode materials of ultracapacitor, and during current density 5A/g, its initial specific capacities can reach 190F/g, and circulate 10000 times, capability retention is 96.3%.
In order to understand the present invention further, below in conjunction with embodiment, the preparation method to nitrogen-doped graphene provided by the invention is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Get the graphene oxide colloid 100ml that concentration is 1mg/ml, then mix postlyophilization with 1g bicarbonate of ammonia, the powder obtained is placed in sealed vessel and is heated to 100 DEG C, insulation 5h.Question response terminates, and opens reactor after being cooled to room temperature, namely obtains black product nitrogen-doped graphene.
As shown in Figure 1, Fig. 1 is the transmission electron microscope picture of nitrogen-doped graphene prepared by embodiment 1, and as shown in Figure 1, the nitrogen-doped graphene laminated structure that the present invention obtains is complete.As shown in Figure 2, Fig. 2 is the TEM selected area electron diffraction figure of nitrogen-doped graphene, and the nitrogen-doped graphene crystalline network that obtains of the present invention is complete as shown in Figure 2.As shown in Figure 3, Fig. 3 is x-ray photoelectron energy spectrogram, in figure, curve a is the x-ray photoelectron spectrum curve of graphene oxide, curve b is the x-ray photoelectron spectrum curve of nitrogen-doped graphene prepared by embodiment 1, in figure, curve e is the x-ray photoelectron spectrum curve of Graphene, from curve b, after reaction 5h, in Graphene, there is obvious nitrogen-doping peak.As shown in Figure 4, Fig. 4 is the XPS swarming spectrogram of N1s in nitrogen-doped graphene, and containing three kinds of different N doping forms in nitrogen-doped graphene, curve a, b and c are respectively pyridine-N, the XPS curve of pyrroles-N and graphite-N.As shown in Figure 5, the electrochemistry cyclic curve figure of Fig. 5 to be nitrogen-doped graphene be ultracapacitor of electrode materials, as shown in Figure 5, nitrogen-doped graphene its initial specific capacities under current density 5A/g condition can reach 190F/g, circulate 10000 times, capability retention is 96.3%.
Embodiment 2
Get the graphene oxide colloid 100ml that concentration is 5mg/ml, then mix postlyophilization with 100mg volatile salt, the powder obtained is placed in sealed vessel and is heated to 200 DEG C, insulation 10h.Question response terminates, and opens reactor after being cooled to room temperature, namely obtains black product nitrogen-doped graphene.
As shown in Figure 3, Fig. 3 is the x-ray photoelectron energy spectrogram of nitrogen-doped graphene prepared by embodiment 2, and in figure, curve c is the x-ray photoelectron spectrum curve of nitrogen-doped graphene prepared by the present embodiment, from curve c, after reaction 10h, in Graphene, there is obvious nitrogen-doping peak.
Embodiment 3
Get the Graphene colloid 100ml that concentration is 10mg/ml, then mix postlyophilization with 100mg volatile salt, the powder obtained is placed in sealed vessel and is heated to 300 DEG C, insulation 20h.Question response terminates, and opens reactor after being cooled to room temperature, namely obtains black product nitrogen-doped graphene.
As shown in Figure 3, Fig. 3 is the x-ray photoelectron energy spectrogram of nitrogen-doped graphene prepared by embodiment 3, and in figure, curve d is the x-ray photoelectron spectrum curve of nitrogen-doped graphene prepared by the present embodiment, from curve d, after reaction 20h, there is obvious nitrogen-doping peak in Graphene.
Embodiment 4
Get the graphene oxide colloid 100ml that concentration is 10mg/ml, then mix postlyophilization with 50mg urea, the powder obtained is placed in sealed vessel and is heated to 250 DEG C, insulation 8h.Question response terminates, and opens reactor after being cooled to room temperature, namely obtains black product nitrogen-doped graphene.
By the electrode materials of nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, ultracapacitor its initial specific capacities under current density 5A/g condition can reach 180F/g, and circulate 10000 times, capability retention is 92%.
Embodiment 5
Get the graphene oxide colloid 100ml that concentration is 15mg/ml, then mix postlyophilization with 300mg Silver Nitrate, the powder obtained is placed in sealed vessel and is heated to 300 DEG C, insulation 30h.Question response terminates, and opens reactor after being cooled to room temperature, and products therefrom is used dust technology and washed with de-ionized water repeatedly, and namely final drying process obtains black product nitrogen-doped graphene.
By the electrode materials of nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, ultracapacitor its initial specific capacities under current density 5A/g condition can reach 185F/g, and circulate 10000 times, capability retention is 90%.
Embodiment 6
Get the graphene oxide colloid 100ml that concentration is 15mg/ml, then mix postlyophilization with 30mg primary ammonium phosphate, the powder obtained is placed in sealed vessel and is heated to 300 DEG C, insulation 15h.Question response terminates, and opens reactor, products therefrom is used washed with de-ionized water repeatedly after being cooled to room temperature, and namely final drying process obtains black product nitrogen-doped graphene.
By the electrode materials of nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, ultracapacitor its initial specific capacities under current density 5A/g condition can reach 180F/g, and circulate 10000 times, capability retention is 89%.
Embodiment 7
Get the graphene oxide colloid 100ml that concentration is 10mg/ml, then mix postlyophilization with 100mg urea, 100mg potassium hydroxide, put into encloses container, then pass into the nitrogen deoxygenation of purity >=99%, sealed vessel after 2 minutes.Reaction vessel is placed in air dry oven and is warming up to 150 DEG C, keep 15h.Question response terminates, and opens reactor, products therefrom is used washed with de-ionized water repeatedly after being cooled to room temperature, and namely final drying process obtains black product nitrogen-doped graphene.
By the electrode materials of nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, ultracapacitor its initial specific capacities under current density 5A/g condition can reach 190F/g, and circulate 10000 times, capability retention is 92.5%.
Embodiment 8
Get the graphene oxide colloid 100ml that concentration is 10mg/ml, then mix postlyophilization with 100mg urea, 1.1g zinc chloride, put into encloses container, then pass into the argon gas deoxygenation of purity >=99%, sealed vessel after 2 minutes.Reaction vessel is placed in air dry oven and is warming up to 270 DEG C, keep 25h.Question response terminates, and opens reactor, products therefrom is used washed with de-ionized water repeatedly after being cooled to room temperature, and namely final drying process obtains black product nitrogen-doped graphene.
By the electrode materials of nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, ultracapacitor its initial specific capacities under current density 5A/g condition can reach 190F/g, and circulate 10000 times, capability retention is 93%.
Embodiment 9
Get the graphene oxide colloid 100ml that concentration is 8mg/ml, then mix postlyophilization with 40mg trimeric cyanamide, 100mg potassium hydroxide, put into encloses container, then pass into the argon gas deoxygenation of purity >=99%, sealed vessel after 2 minutes.Reaction vessel is placed in air dry oven and is warming up to 180 DEG C, keep 18h.Question response terminates, and opens reactor, products therefrom is used washed with de-ionized water repeatedly after being cooled to room temperature, and namely final drying process obtains black product nitrogen-doped graphene.
By the electrode materials of nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, ultracapacitor its initial specific capacities under current density 5A/g condition can reach 180F/g, and circulate 10000 times, capability retention is 89%.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (3)
1. a preparation method for nitrogen-doped graphene, is characterized in that, comprising:
Carbon material and the compound containing active nitrogen element are placed in encloses container, be heated to 100 ~ 300 DEG C, nitrogen-doped graphene is obtained after reaction, the described compound containing active nitrogen element is gas and/or solid, the described compound containing active nitrogen element is nitrogen protoxide, nitrogen peroxide, volatile salt, bicarbonate of ammonia, primary ammonium phosphate, urea, one or more of trimeric cyanamide and Silver Nitrate, described carbon material is Graphene or graphene oxide, the mass ratio of described Graphene or graphene oxide and the described compound containing active nitrogen element is 0.1:1 ~ 50:1, also activator is comprised in described encloses container, described activator is zinc chloride, potassium hydroxide or phosphoric acid,
The mass ratio of described carbon material and described activator is 0.1:1 ~ 10:1;
The time of described reaction is 0.5 ~ 30h.
2. preparation method according to claim 1, is characterized in that, the preparation method of described graphene oxide is:
Be the ultrasonic 0.5 ~ 2h of graphene oxide colloid of 1mg/ml ~ 15mg/ml by concentration, lyophilize, obtains graphene oxide.
3. preparation method according to claim 1, is characterized in that, is full of protective gas in described encloses container.
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| CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
| CN102502593A (en) * | 2011-10-11 | 2012-06-20 | 中国石油大学(北京) | Preparation method of grapheme or doped graphene or graphene complex |
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| CN106882794A (en) * | 2017-03-24 | 2017-06-23 | 杭州格蓝丰纳米科技有限公司 | A kind of preparation method of nitrogen-doped graphene |
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