CN103626158A - Preparation method of nitrogen doped graphene and application of nitrogen doped graphene - Google Patents
Preparation method of nitrogen doped graphene and application of nitrogen doped graphene Download PDFInfo
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Abstract
The invention provides a preparation method of nitrogen doped graphene and an application of the nitrogen doped graphene in super capacitors. The preparation method of the nitrogen doped graphene specifically comprises the following steps: putting a carbon material and a compound containing active nitrogen elements in an enclosed container, and heating to a temperature of 100 to 300 DEG C so as to obtain the nitrogen doped graphene. In the preparation process of the nitrogen doped graphene, under a heating condition, nitrogen elements in the compound containing active nitrogen elements are mixed into the carbon material so as to obtain the nitrogen doped graphene. The nitrogen doped graphene preparation method mentioned above avoids adopting a high reaction temperature, and has the advantages of mild preparation conditions and low production cost. The prepared nitrogen doped graphene is used as an electrode material of a super capacitor, and the specific capacity of the super capacitor can reach 190 F/g, when the electric current density is 5 A/g. The capacity retention ratio is 96.3% after 10000 times of circulation.
Description
Technical field
The present invention relates to Graphene technical field, relate in particular to preparation method and the application thereof of nitrogen-doped graphene.
Background technology
Graphene is comprised of carbon six-ring, there is the cellular lattice structure of two-dimension periodic, the two-dirnentional structure of this uniqueness, make it have the physics-chem characteristic of high intensity, good electroconductibility and fabulous various excellences such as light transmission, so 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 adjusting semiconductor material Electronic Performance, and research shows, Graphene energy band structure after doping is adjusted, thereby makes the range of application of Graphene have great expansion, and also raising accordingly of performance.For example: the electrode materials using the Graphene after doping as ultracapacitor, not only electroconductibility increases, and heteroatomic mixing also can produce fake capacitance, further improves the specific storage of electrical condenser.Therefore the doping of Graphene has become the focus that the numerous subject investigators of physics, chemistry and materialogy pay close attention to.
2009 Nian，Liu Yun boundary seminar reported first the preparation method of nitrogen-doped graphene.Author adopts chemical Vapor deposition process, usings ammonia as nitrogenous source, and methane, as carbon source, is incubated 10min at 800 ℃, has prepared which floor nitrogen-doped graphene of minority.At present, existing doped graphene is mainly nitrogen doping, for example, take graphene oxide as raw material, take ammonia as nitrogenous source, carry out high temperature annealing and make nitrogen-doped graphene, this method is prepared the temperature that nitrogen-doped graphene needs are higher, 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 to provide a kind of preparation method 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 that contains active nitrogen element are placed in to encloses container, be heated to 100 ~ 300 ℃, after reaction, obtain nitrogen-doped graphene, described in contain active nitrogen element compound be gas and/or solid, described carbon material is Graphene or graphene oxide.
Preferably, the preparation method of described graphene oxide is:
Ultrasonic 0.5 ~ the 2h of graphene oxide colloid that is 1mg/ml ~ 15mg/ml by concentration, lyophilize, obtains graphene oxide.
Preferably, in described encloses container, also comprise activator.
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 compound that contains active nitrogen element described in is one or more of nitrogen protoxide, nitrogen peroxide, volatile salt, bicarbonate of ammonia, primary ammonium phosphate, urea, trimeric cyanamide and Silver Nitrate.
Preferably, in described encloses container, be full of protective gas.
Preferably, the time of described reaction is 0.5 ~ 30h.
Preferably, described Graphene or graphene oxide and described in contain active nitrogen element the mass ratio of compound be 0.1:1 ~ 50:1.
The application of nitrogen-doped graphene described in such scheme in preparing the electrode materials of ultracapacitor.
The preparation method who the invention provides a kind of nitrogen-doped graphene, is specially: carbon material and the compound that contains active nitrogen element are placed in to encloses container, are heated to 100 ~ 300 ℃, obtain nitrogen-doped graphene after reaction.In preparing the process of nitrogen-doped graphene, under heating condition, the nitrogen-doping in the compound that contains active nitrogen element is entered in carbon material, thereby obtain nitrogen-doped graphene.The present invention reacts the compound that contains active nitrogen element in airtight environment with carbon material, increased the pressure of encloses container, is conducive to promote active nitrogen element to adulterate, thereby nitrogen element just can be adulterated at lower temperature.The present invention adopts aforesaid method to prepare nitrogen-doped graphene, avoided adopting higher temperature of reaction, thereby make preparation condition gentleness and production cost lower.Azepine Graphene prepared by the present invention 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 in nitrogen-doped graphene (1s);
Fig. 5 is the cyclic curve figure of nitrogen-doped graphene electrode materials under current density 5A/g condition.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than 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 that contains active nitrogen element are placed in to encloses container, be heated to 100 ~ 300 ℃, after reaction, obtain nitrogen-doped graphene, described in contain active nitrogen element compound be gas and/or solid, described carbon material is Graphene or graphene oxide.
According to the present invention, in the above-mentioned process of preparing nitrogen-doped graphene, described graphene oxide is preparation as follows specifically:
The graphene oxide colloid that is 1mg/ml ~ 15mg/ml by concentration, after ultrasonic 0.5 ~ 2h, lyophilize, obtains graphene oxide.In order to guarantee 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: by after thing quick freezing to be dried, then the drying means of under high vacuum condition, ice distillation wherein being removed for water vapour.The present invention, by after graphene oxide sonic oscillation, carries out lyophilize, water is wherein removed, and effectively guaranteed the activity of graphene oxide, has obtained graphene oxide.For the compound that contains active nitrogen element described in increasing and the contact area of described carbon material, farthest reduce the nitrogen needed temperature of reaction of adulterating, as preferred version, by described carbon material with described in contain active nitrogen element compound evenly after, carry out again lyophilize, obtain after 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 that contains active nitrogen element is gas and/or solid, is preferably one or more of nitrogen protoxide, nitrogen peroxide, volatile salt, bicarbonate of ammonia, primary ammonium phosphate, urea and trimeric cyanamide.The above-mentioned gas that contains active nitrogen element is placed in encloses container and produces pressure, can increase the pressure of encloses container, thereby reduce the energy of reaction, make the active nitrogen wherein containing be easy to be entrained in Graphene, and above-mentioned primary ammonium phosphate, urea and trimeric cyanamide are under heating condition, decomposite ammonia, thereby in Graphene, carry out nitrogen doping, contain in addition volatile salt in the solid of active nitrogen element under heating condition, split the carbon dioxide off and ammonia, carbonic acid gas has activation to carbon material Graphene or graphene oxide, increase the reactive behavior of carbon material, make nitrogen doping be easy to carry out, carbonic acid gas and ammonia have increased the pressure of encloses container simultaneously, more easily carry out nitrogen doping, thereby nitrogen is entrained at lower temperature.Same for the bicarbonate of ammonia that contains active nitrogen element, under heating condition, split the carbon dioxide off, water vapour and ammonia, carbonic acid gas and water vapour have activation to carbon material Graphene or graphene oxide, greatly increased the reactive behavior of carbon material, made nitrogen doping be easy to carry out, carbonic acid gas, water vapour and ammonia have increased the pressure of encloses container simultaneously, more easily carry out nitrogen doping, thereby nitrogen is entrained at lower temperature.According to the present invention, described in contain active nitrogen element compound more preferably bicarbonate of ammonia or volatile salt.
In order to reduce the energy of reaction needed, make nitrogen doping reaction be easy to carry out, the present invention also comprises activator in the process of carrying out nitrogen 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, can improve the reactive behavior of carbon, thus needed energy while having reduced nitrogen-doping; In encloses container, described carbonic acid gas or water vapour also can increase the pressure of encloses container simultaneously, reaction is more easily carried out, thereby made nitrogen be easy to be doped in Graphene.And for described zinc chloride, potassium hydroxide or phosphoric acid, it mainly plays activation, can increase the reactive behavior of carbon, thus the reactive behavior while having reduced nitrogen-doping.According to the present invention, described activator is preferably carbonic acid gas or water vapour.
The compound of the present invention by containing active nitrogen element described in regulating and the mass ratio of described carbon material, reach the object of controlling nitrogen content in nitrogen-doped graphene, and the mass ratio of described carbon material and described ammonium salt is preferably 1:30 ~ 10:1, more preferably 1:5 ~ 2:1.
The present invention is preferably full of protective gas in encloses container; it is oxidized in order to prevent carbon material that raw material is placed in to protective atmosphere; described protective atmosphere is preferably rare gas element or nitrogen; described protective atmosphere is argon gas or nitrogen more preferably, and described protective atmosphere most preferably is purity and is more than or equal to 99% argon gas or nitrogen.Described encloses container is preferably withstand voltage encloses container, because the solid that contains active nitrogen element may decomposite ammonia, water or other gas under heating condition, above-mentioned gas can produce pressure in encloses container, therefore described encloses container need to bear certain pressure, certainly the required pressure bearing not is high pressure, in order to reduce costs, the maximum of described encloses container is born pressure and is preferably 2 ~ 3MPa.The temperature of described heating is 100 ~ 300 ℃, is preferably 150 ~ 250 ℃, and the time of described heating is preferably 0.5 ~ 30h, more preferably 5 ~ 20h.If Heating temperature is too low or heat-up time is too short, the nitrogen content in nitrogen-doped graphene is very few, thereby affects the performance of nitrogen-doped graphene.
In preparing the process of nitrogen-doped graphene, as preferred version, first the present invention is placed in reactor by described activator, carbon material and the compound that contains active nitrogen element, pass into purity and be not less than 99% argon gas to remove the oxygen in reactor, thereby avoid raw material oxidized, subsequently encloses container; Again encloses container is preferably placed in to air dry oven or retort furnace is heated to 100 ~ 300 ℃, reacts, after reaction finishes, cooling, obtain nitrogen-doped graphene.
The compound that the present invention be take carbon material and contained active element is raw material, above-mentioned raw materials is heated to 100 ~ 300 ℃, make a large amount of functional groups on graphene oxide surface, as functional group's decomposition-reductions such as carboxyl, epoxy group(ing), hydroxyls, the gas and/or the solid that contain active nitrogen element decompose simultaneously, produce nitrogen element, under heating condition, nitrogen enters nitrogen doping occurs in Graphene, thereby obtains nitrogen-doped graphene.In preparing the process of nitrogen-doped graphene, the mass ratio of the temperature heating by adjusting, time and raw material, thus reach the object of controlling nitrogen doping.
Nitrogen-doped graphene prepared by the present invention is applied to prepare the electrode materials of ultracapacitor, can effectively 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 storage can reach 190F/g, circulates 10000 times, and capability retention is 96.3%.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of nitrogen-doped graphene provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Getting concentration is the graphene oxide colloid 100ml of 1mg/ml, then mixes postlyophilization with 1g bicarbonate of ammonia, the powder obtaining is placed in to sealed vessel and is heated to 100 ℃, insulation 5h.Question response finishes, and opens reactor after being cooled to room temperature, obtains black Nitrogen in Products doped graphene.
As shown in Figure 1, Fig. 1 is the transmission electron microscope picture of the nitrogen-doped graphene of embodiment 1 preparation, and as shown in Figure 1, the nitrogen-doped graphene laminated structure that the present invention obtains is complete.As shown in Figure 2, the TEM selected area electron diffraction figure that Fig. 2 is nitrogen-doped graphene, the nitrogen-doped graphene crystalline network that the present invention obtains is as shown in Figure 2 complete.As shown in Figure 3, Fig. 3 is x-ray photoelectron energy spectrogram, the x-ray photoelectron spectrum curve that in figure, curve a is graphene oxide, curve b is the x-ray photoelectron spectrum curve of the nitrogen-doped graphene of embodiment 1 preparation, the x-ray photoelectron spectrum curve that in figure, curve e is 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, contains three kinds of different nitrogen doped forms in nitrogen-doped graphene, and curve a, b and c are respectively pyridine-N, the XPS curve of pyrroles-N and graphite-N.As shown in Figure 5, Fig. 5 is that nitrogen-doped graphene is the electrochemistry cyclic curve figure of the ultracapacitor of electrode materials, and as shown in Figure 5, nitrogen-doped graphene its initial specific storage under current density 5A/g condition can reach 190F/g, circulate 10000 times, capability retention is 96.3%.
Embodiment 2
Getting concentration is the graphene oxide colloid 100ml of 5mg/ml, then mixes postlyophilization with 100mg volatile salt, the powder obtaining is placed in to sealed vessel and is heated to 200 ℃, insulation 10h.Question response finishes, and opens reactor after being cooled to room temperature, obtains black Nitrogen in Products doped graphene.
As shown in Figure 3, Fig. 3 is the x-ray photoelectron energy spectrogram of the nitrogen-doped graphene of embodiment 2 preparation, and in figure, curve c is the x-ray photoelectron spectrum curve of the nitrogen-doped graphene prepared of the present embodiment, from curve c, after reaction 10h, in Graphene, there is obvious nitrogen-doping peak.
Embodiment 3
Getting concentration is the Graphene colloid 100ml of 10mg/ml, then mixes postlyophilization with 100mg volatile salt, the powder obtaining is placed in to sealed vessel and is heated to 300 ℃, insulation 20h.Question response finishes, and opens reactor after being cooled to room temperature, obtains black Nitrogen in Products doped graphene.
As shown in Figure 3, Fig. 3 is the x-ray photoelectron energy spectrogram of the nitrogen-doped graphene of embodiment 3 preparation, and in figure, curve d is the x-ray photoelectron spectrum curve of the nitrogen-doped graphene prepared of the present embodiment, from curve d, after reaction 20h, there is obvious nitrogen-doping peak in Graphene.
Embodiment 4
Getting concentration is the graphene oxide colloid 100ml of 10mg/ml, then mixes postlyophilization with 50mg urea, the powder obtaining is placed in to sealed vessel and is heated to 250 ℃, insulation 8h.Question response finishes, and opens reactor after being cooled to room temperature, obtains black Nitrogen in Products doped graphene.
Electrode materials by nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, and ultracapacitor its initial specific storage under current density 5A/g condition can reach 180F/g, circulates 10000 times, and capability retention is 92%.
Embodiment 5
Getting concentration is the graphene oxide colloid 100ml of 15mg/ml, then mixes postlyophilization with 300mg Silver Nitrate, the powder obtaining is placed in to sealed vessel and is heated to 300 ℃, insulation 30h.Question response finishes, and opens reactor after being cooled to room temperature, and products therefrom is used to rare nitric acid and washed with de-ionized water repeatedly, and final drying is processed and obtained black Nitrogen in Products doped graphene.
Electrode materials by nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, and ultracapacitor its initial specific storage under current density 5A/g condition can reach 185F/g, circulates 10000 times, and capability retention is 90%.
Embodiment 6
Getting concentration is the graphene oxide colloid 100ml of 15mg/ml, then mixes postlyophilization with 30mg primary ammonium phosphate, the powder obtaining is placed in to sealed vessel and is heated to 300 ℃, insulation 15h.Question response finishes, and opens reactor after being cooled to room temperature, and products therefrom is used to washed with de-ionized water repeatedly, and final drying is processed and obtained black Nitrogen in Products doped graphene.
Electrode materials by nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, and ultracapacitor its initial specific storage under current density 5A/g condition can reach 180F/g, circulates 10000 times, and capability retention is 89%.
Embodiment 7
Getting concentration is the graphene oxide colloid 100ml of 10mg/ml, then mixes postlyophilization with 100mg urea, 100mg potassium hydroxide, puts into encloses container, then passes 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 ℃, keep 15h.Question response finishes, and opens reactor after being cooled to room temperature, and products therefrom is used to washed with de-ionized water repeatedly, and final drying is processed and obtained black Nitrogen in Products doped graphene.
Electrode materials by nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, and ultracapacitor its initial specific storage under current density 5A/g condition can reach 190F/g, circulates 10000 times, and capability retention is 92.5%.
Embodiment 8
Getting concentration is the graphene oxide colloid 100ml of 10mg/ml, then mixes postlyophilization with 100mg urea, 1.1g zinc chloride, puts into encloses container, then passes 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 ℃, keep 25h.Question response finishes, and opens reactor after being cooled to room temperature, and products therefrom is used to washed with de-ionized water repeatedly, and final drying is processed and obtained black Nitrogen in Products doped graphene.
Electrode materials by nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, and ultracapacitor its initial specific storage under current density 5A/g condition can reach 190F/g, circulates 10000 times, and capability retention is 93%.
Embodiment 9
Getting concentration is the graphene oxide colloid 100ml of 8mg/ml, then mixes postlyophilization with 40mg trimeric cyanamide, 100mg potassium hydroxide, puts into encloses container, then passes 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 ℃, keep 18h.Question response finishes, and opens reactor after being cooled to room temperature, and products therefrom is used to washed with de-ionized water repeatedly, and final drying is processed and obtained black Nitrogen in Products doped graphene.
Electrode materials by nitrogen-doped graphene for the preparation of ultracapacitor, electro-chemical test shows, and ultracapacitor its initial specific storage under current density 5A/g condition can reach 180F/g, circulates 10000 times, and capability retention is 89%.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.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 improvement and modification also fall in the protection domain of the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for nitrogen-doped graphene, is characterized in that, comprising:
Carbon material and the compound that contains active nitrogen element are placed in to encloses container, be heated to 100 ~ 300 ℃, after reaction, obtain nitrogen-doped graphene, described in contain active nitrogen element compound be gas and/or solid, described carbon material is Graphene or graphene oxide.
2. preparation method according to claim 1, is characterized in that, the preparation method of described graphene oxide is:
Ultrasonic 0.5 ~ the 2h of graphene oxide colloid that is 1mg/ml ~ 15mg/ml by concentration, lyophilize, obtains graphene oxide.
3. preparation method according to claim 1, is characterized in that, also comprises activator in described encloses container.
4. preparation method according to claim 3, is characterized in that, described activator is water vapour, carbonic acid gas, zinc chloride, potassium hydroxide or phosphoric acid.
5. preparation method according to claim 3, is characterized in that, the mass ratio of described carbon material and described activator is 0.1:1 ~ 10:1.
6. preparation method according to claim 1, is characterized in that, described in contain active nitrogen element compound be one or more of nitrogen protoxide, nitrogen peroxide, volatile salt, bicarbonate of ammonia, primary ammonium phosphate, urea, trimeric cyanamide and Silver Nitrate.
7. preparation method according to claim 1, is characterized in that, in described encloses container, is full of protective gas.
8. preparation method according to claim 1, is characterized in that, the time of described reaction is 0.5 ~ 30h.
9. preparation method according to claim 1, is characterized in that, described Graphene or graphene oxide and described in contain active nitrogen element the mass ratio of compound be 0.1:1 ~ 50:1.
10. the application of the nitrogen-doped graphene described in claim 1 ~ 9 any one in preparing the electrode materials of ultracapacitor.
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