CN109775693A - A kind of preparation method of nitrogen-doped graphene material - Google Patents
A kind of preparation method of nitrogen-doped graphene material Download PDFInfo
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Abstract
The invention belongs to functionalization graphene preparation fields, disclose a kind of preparation method of nitrogen-doped graphene material, comprising the following steps: (1) graphene oxide is dispersed in polar solvent and obtains dispersion liquid；(2) then stirring plus alkali adjust pH >=9；(3) nitrogen-doping compound and condensing agent is added in the reaction system obtained by step (2), after being stirred to react a period of time, cleaning is drying to obtain nitrogen-doped graphene material.Nitrogen-doped graphene material nitrogen element content with higher produced by the present invention and excellent chemical property.
Description
Technical field
The invention belongs to functionalization graphene preparation fields, and in particular to a kind of preparation side of nitrogen-doped graphene material
Method.
Background technique
Graphene is the two-dimentional carbon nano-structured material being made of mono-layer graphite piece, because of it with high specific surface area and
Brilliant electricity, optics, calorifics and mechanical performance is led in solar battery, supercapacitor, battery, sensor and actuator
There are huge potential applications in domain.
Unreduced graphene, that is, surface of graphene oxide contains hydroxyl, epoxy group, carbonyl, carboxyl and five yuan/hexa-atomic
Aromatic region (the sp of hydroxy functional group random distribution2Carbon atom) and oxidation of fat race region (sp3Carbon atom).Organic group
By being covalently attached with the oxygen-containing functional group of surface of graphene oxide, formation Graphene derivative, thus regulate and control graphene-structured,
Improve the dispersibility of graphene, changes the performances such as graphene light, electricity, magnetic.Therefore, carrying out functionalization to graphene is to study at present
The focus of attention, wherein about the N doping that dehydration condensation preparation occurs by amino and surface of graphene oxide carboxyl
Graphene has been used to improve electro-catalysis and electrochemical field.
Have much for the preparation research of nitrogen-doped graphene both at home and abroad at present, the most common method is to use thionyl chloride
(SOCl2) carboxyl on active oxidation graphene, reaction generates acid chloride groups.For example, Gogotsiet et al. is in J. Am.
Chem.Soc., it is reported on 2009,131,4594-4595 with octadecylamine (ODA) covalent functionalization graphene, first
Chloride derivative is separated, washs, the washing, purifying, drying of excessive ODA is then reacted and used with ODA, whole process is held
The continuous time is up to several days；Natalia et al. proposes a kind of without molten on RSC Adv., 2016,6,113596-113610
The method of agent one-step synthesis, synthesis process does not need additional reagent activation, without using toxic SOCl2.Its uniqueness
Be in amido bond is that thermal activation is formed at 150-180 DEG C, but the universality of this method is not strong, and amido bond is in height
It is unstable under temperature to be easily broken off.
The existing nitrogen source for preparing nitrogen-doped graphene contains a small amount of amido (one or two) mostly.Li Sun etc.
People is mixed on RSC Advances, 2012,2,4498-4506 by the hydro-thermal reaction synthetic nitrogen of graphene oxide and urea
Miscellaneous graphene nanometer sheet, in water-heat process, the nitrogen dopant of urea can be with sustained release NH3And it is oxygen-containing with graphene oxide
Functional group reactions, subsequent nitrogen atom doping is into graphene skeleton.Likewise, Haiwei Wu et al. is in Chemical
The addition of pyrroles has also been inquired into using urea and pyrroles as nitrogen source in 855-867 in Engineering Journal, 327 (2017)
Measure the influence to graphene-structured.The experimental results showed that can not observe graphite in scanning electron microscope as the pyrroles of excessive addition
The lamellar structure of alkene, this is because foring stronger interaction between excessive pyrroles.However containing there are three and the above amine
The research and its application of base are rarely reported.
Summary of the invention
Higher and electrochemical performance the nitrogen-doped graphene the purpose of the present invention is to provide a kind of nitrogen element content
The preparation method of material.
To achieve the above object, the present invention adopts the following technical scheme: a kind of preparation method of nitrogen-doped graphene material,
The following steps are included: graphene oxide is dispersed in polar solvent and obtains dispersion liquid by (1)；(2) then stirring plus alkali adjust pH
≥9；(3) nitrogen-doping compound and condensing agent is added in the reaction system obtained by step (2), is stirred to react a period of time
Afterwards, it cleans, is drying to obtain nitrogen-doped graphene material.
Further, the nitrogen-doping compound is three aminated compounds.
Further, three aminated compounds is three (2- amino-ethyl) amine, three (4- aminophenyl) amine or 1,3,5-
Three (4- aminophenyl) benzene.
Further, the condensing agent is the mixture of dicyclohexylcarbodiimide and I-hydroxybenzotriazole.
Further, the molar ratio of dicyclohexylcarbodiimide and I-hydroxybenzotriazole is 1:1 in the condensing agent.
Further, the alkali is sodium hydroxide, and the mass ratio of sodium hydroxide and graphene oxide is 1:1, sodium hydroxide,
The molar ratio of condensing agent and nitrogen-doping compound is 7.5:(6.0~6.5): (1.0~3.5), preferably 7.5:6.2:
(1.03~3.1).
Further, in step (3), 15~30 DEG C of reaction temperature, the reaction time 24 hours, cleaning process used polarity respectively
Alternately cleaning at least twice, is dried in vacuo 36~48 hours at 60 DEG C~80 DEG C for solvent and water.
Further, in step (1), the polar solvent is dispersion in n,N-Dimethylformamide or dimethyl sulfoxide
Process is that ultrasonic disperse mixes 30~45 minutes.
Further, in step (2), 15~30 DEG C of whipping temp, mixing time 1 hour, pH was 11~12.
Compared with prior art, the present invention has following technical effect that
(1) process of the present invention is simple, and reaction temperature is low, can carry out especially at 15~30 DEG C, saves energy consumption of reaction, reduces
Preparation cost；It discharges during simultaneous reactions without toxic and harmful gas, not only economized on resources, but also protection environment；Gained N doping stone
The nitrogen element content of black alkene material is higher, between 3% ~ 14%；And the nitrogen-doped graphene material prepared has excellent
Chemical property, head are put between 579.5 ~ 1062.8mAh/g of specific capacity, and under 0.2C current density, circulation after 50 weeks, protect by capacity
Holdup is 40% or more.
(2) with using two amine molecules, the application uses the molecule with triamine as nitrogen-doping compared with raw material
Close object, can on the surface of graphene on form more chemical bonds, can be formed on nitrogen-doped graphene material more stable intrinsic
Type 3D network.
(3) it is carried out in acidic environment mostly in the prior art, and the application overcomes technology prejudice, selects in alkaline environment
Lower reaction, sodium hydroxide can be reacted with the carboxylic acid of surface of graphene oxide, formed carboxylate, activated graphene oxide
The carboxylic acid on surface, and then amidation process is made to be easier to carry out.
Detailed description of the invention
Fig. 1 is three (4- aminophenyl) amine-graphene oxide infrared spectrograms prepared by embodiment 1；
Fig. 2 is three (4- aminophenyl) amine-graphene oxide Raman spectrograms prepared by embodiment 1；
Fig. 3 is that the x-ray photoelectron spectroscopy of three (4- aminophenyl) amine-graphene oxide C elements prepared by embodiment 1 is fitted peak
Figure；
Fig. 4 is that the x-ray photoelectron spectroscopy of three (4- aminophenyl) amine-graphene oxide N elements prepared by embodiment 1 is fitted peak
Figure；
Fig. 5 is the X-ray photoelectron spectroscopic analysis figure of Examples 1 to 5；
Fig. 6 is the GO-TAPA of embodiment 13.1mmolThe first all charging and discharging curve figures of the Li-S battery of@S cathode assembling；
Fig. 7 is the GO-TAPA of embodiment 13.1mmolThe Li-S circulating battery stability and coulombic efficiency figure of@S cathode assembling；
Fig. 8 is the GO-TAPA of embodiment 22.06mmolThe first all charging and discharging curve figures of the Li-S battery of@S cathode assembling；
Fig. 9 is the GO-TAPA of embodiment 22.06mmolThe Li-S circulating battery stability and coulombic efficiency figure of@S cathode assembling；Figure
10 be the GO-TAPA of embodiment 31.03mmolThe first all charging and discharging curve figures of the Li-S battery of@S cathode assembling；
Figure 11 is the GO-TAPA of embodiment 31.03mmolThe Li-S circulating battery stability and coulombic efficiency figure of@S cathode assembling；
Figure 12 is the first all charging and discharging curve figures of the Li-S battery of the GO-TAEA@S cathode assembling of embodiment 4；
Figure 13 is the Li-S circulating battery stability and coulombic efficiency figure of the GO-TAEA@S cathode assembling of embodiment 4；
Figure 14 is the first all charging and discharging curve figures of the Li-S battery of the GO-TAPB@S cathode assembling of embodiment 5；
Figure 15 is the Li-S circulating battery stability and coulombic efficiency figure of the GO-TAPB@S cathode assembling of embodiment 5；
Figure 16 is that different content three (4- aminophenyl) amine-graphene oxide X-ray diffraction prepared by embodiment 1,2,3 compares
Figure；
Figure 17~19 are three (4- aminophenyl) amine-graphene oxide scanning electron microscope of different content prepared by embodiment 1,2,3
Figure；
Figure 20 is that the X-ray diffraction of identical, the different nitrogen-doping compound preparation of 1,4,5 content of embodiment compares figure.
In figure, 1 is GO-TAPA3.1mmol, 2 be GO-TAPA2.06mmol, 3 be GO-TAPA1.03mmol, 4 be GO-TAEA, and 5 are
GO-TAPB, a are that electric discharge proportion is held, and b is that charging proportion is held, and c is coulombic efficiency.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
Embodiment 1
A kind of preparation method of nitrogen-doped graphene material, comprising the following steps:
(1) at 15~30 DEG C, 0.3g graphene oxide is added in 30mL n,N-Dimethylformamide (DMF), ultrasound point
Mixing 30 minutes is dissipated, brown color dispersion liquid is obtained；
(2) then, stirring be added (7.5mmol, 0.3g) sodium hydrate particle, adjust reaction system acid-base property be pH=11~
12, it is stirred 1 hour at 15~30 DEG C；
(3) 3.1mmol tri- (4- aminophenyl) amine, 3.1mmol dicyclohexyl carbon two is added in the reaction system obtained by step (2)
Imines (DCC) and 3.1mmol1- hydroxybenzotriazole (Hobt) after stirring 24 hours at 15~30 DEG C, use N, N- bis- respectively
Methylformamide (DMF) and deionized water are centrifuged repeatedly cleaning three times, are then placed in vacuum oven, and dry 48 is small at 60 DEG C
When, nitrogen-doped graphene material is obtained, sample 1 is denoted as.Through detecting, nitrogen content is that 11.33%, head puts specific capacity and is in sample 1
619.3 mAh/g, capacity retention ratio is 61.9%.
Embodiment 2
Compared with Example 1, difference is: in step (3), three (4- aminophenyl) amine dosages are 2.06mmol, sample obtained
Product are denoted as sample 2.Through detecting, 2 nitrogen content of sample is that put specific capacity be 845 mAh/g to 5.63%, head, and capacity retention ratio is 48%.
Embodiment 3
Compared with Example 1, difference is: in step (3), the dosage of three (4- aminophenyl) amine is 1.03mmol, obtained
Sample is denoted as sample 3.Through detecting, 3 nitrogen content of sample is that put specific capacity be 1062.8 mAh/g to 3.19%, head, and capacity retention ratio exists
45%。
Embodiment 4
Compared with Example 1, difference is: in step (3), nitrogen-doping compound is three (2- amino-ethyl) amine, is made
Sample be denoted as sample 4.Through detecting, 4 nitrogen content of sample is that put specific capacity be 701.6 mAh/g, capacity retention ratio to 13.35%, head
42%.
Embodiment 5
Compared with Example 1, difference is: in step (3), nitrogen-doping compound is 1,3,5- tri- (4- aminophenyls)
Benzene, sample obtained are denoted as sample 5.Through detecting, 5 nitrogen content of sample is that put specific capacity be 579.5 mAh/g, capacity to 7.86%, head
Conservation rate is 66%.
1 performance evaluation of sample
Performance evaluation is carried out to gained sample 1, gained infrared spectrogram (FT-IR), Raman spectrogram (Raman), C element X are penetrated
Photoelectron spectra is fitted peak figure and the x-ray photoelectron spectroscopy of N element is fitted peak figure, sees Fig. 1~4 respectively.
GO-TAPA ((the 4- aminobenzene of graphene oxide-three from FT-IR figure shown in FIG. 1, after functional amido
Base) amine) in 3429cm-1The peak at place and the stretching vibration of N-H are related.In 2863cm-1And 2931cm-1There are two new peaks, this
It is due to CH2Symmetrical and asymmetric stretching vibration caused by.Carbonyl peak disappears after functionalization, in 1634cm-1What is occurred is new
Peak, corresponding to the stretching vibration (amide I) of amidocarbonylation C=O, this illustrates GO(graphene oxide) on be connected to amido bond,
And the nitrogen that each nitrogenous compound is had can embody in amido bond, the number of amido bond represents containing for nitrogen
Amount.
It can be seen that, compared to graphene oxide, the D of GO-TAPA is with red shift 2cm from Raman figure shown in Fig. 2-1,
G is with blue shift 8cm-1.G band moves down the electronics transfer enhancing meaned between valence band and conduction band.With GO(0.84) compared with,
The I of GO-TAPAD/IG(0.85) increase shows increasing for disordered structure in GO microstructure, it is also possible to draw in functionalization
Enter sp3Hydridization.
As shown in figure 3, C1s spectrum is made of 4 fitting peaks, in conjunction with energy 284.4,285.4,288.0 and 289.1 eV difference
Corresponding C-C, C-N, C=O and C (O)-O.Peak integration area shows containing more C-N key, shows on GO covalence graft ammonia
Base.
As shown in figure 4, N1s spectrum is made of 2 fitting peaks.Pyridine nitrogen and graphite are respectively corresponded in conjunction with energy 399.1 and 402.2
Nitrogen.Pyridine nitrogen and graphite nitrogen play an important role in the insertion and abjection of lithium ion, and in addition the doping of graphite nitrogen is to graphite
The diffusion of lithium ion has lower resistance in alkene.
1~5 performance evaluation of sample
Infrared spectrum analysis is carried out respectively to sample 2-5, wherein the FT-IR of the FT-IR curve of sample 2 and sample 3 and sample 1 is bent
Line mutually coincide, and carbonyl peak disappears and in 1634cm-1There is the stretching vibration peak (amide corresponding to amidocarbonylation C=O in place
Ⅰ)。
GO-TAEA(graphene oxide-three (2- amino-ethyl) amine of sample 4 and sample 5 after functional amido) (sample
Product 4) in 3429 cm-1The appearance peak at place is related with the stretching vibration of N-H；Carbonyl peak disappears after functionalization, in 1551cm-1It is left
It is right new peak occur ,-NH stretching vibration (amide II) of this peak from C-NH- group；In 1630cm-1Left and right occurs new
Peak, the stretching vibration (amide I) corresponding to amidocarbonylation C=O.Similarly, the GO-TAPB(oxidation after functional amido
Graphene -1,3,5- three (4- aminophenyl) benzene) (sample 5) in 3433 cm-1The appearance peak at place is related with the stretching vibration of N-H；
Carbonyl peak disappears after functionalization, in 1558 cm-1With 1633 cm-1Occur new peak respectively, respectively correspond C-NH- group-
NH stretching vibration (amide II) and the stretching vibration of amidocarbonylation C=O (amide I).This illustrates carboxyl and tri- (2- of TAEA(on GO
Amino-ethyl) amine) and TAPB(1,3,5- tri- (4- aminophenyl) benzene) on amido occur dehydration condensation.
Stablized by X-ray photoelectron spectroscopic analysis figure, the first all charging and discharging curve figures of Li-S battery and Li-S circulating battery
Property and coulombic efficiency figure sample 1~5 is analyzed, Fig. 5 be X-ray photoelectron spectroscopic analysis figure, Fig. 6,8,10,12 and 14 are
The first all charging and discharging curve figures of Li-S battery, Fig. 7,9,11,13 and 15 are Li-S circulating battery stability and coulombic efficiency figure, wherein
Red represents specific discharge capacity, and black represents charge specific capacity, and blue represents coulombic efficiency.
From figure 5 it can be seen that nitrogen content is 11.33% in sample 1, nitrogen content is 5.63% in sample 2, nitrogen in sample 3
Content is 3.19%, and nitrogen content is 13.35% in sample 4, and nitrogen content is 7.86% in sample 5.
As can be seen from Figures 6 and 7, it is 619.3 mAh/g that the head of sample 1, which puts specific capacity, under 0.2 C current density,
After recycling 50 weeks, capacity retention ratio is 61.9%.It is 845 mAh/g that the head that can be seen that sample 2 from Fig. 8 and Fig. 9, which puts specific capacity,
Under 0.2 C current density, circulation is after 50 weeks, and capacity retention ratio is 48%.The head that can be seen that sample 3 from Figure 10 and Figure 11 is put
Specific capacity is 1062.8 mAh/g, and under 0.2 C current density, circulation is after 50 weeks, and capacity retention ratio is 45%.From Figure 12 and figure
13 as can be seen that it is 701.6 mAh/g that the head of sample 4, which puts specific capacity, and under 0.2 C current density, circulation after 50 weeks, protect by capacity
Holdup is 42%.It is 579.5 mAh/g that the head that can be seen that sample 5 from Figure 14 and Figure 15, which puts specific capacity, in 0.2 C current density
Under, circulation is after 50 weeks, and capacity retention ratio is 66%.
1~3 performance evaluation of sample
Compare figure (XRD) and scanning electron microscope (SEM) photograph by X-ray diffraction to compare and analyze sample 1~3, XRD diagram is shown in Figure 16, sweeps
It retouches electron microscope and sees Figure 17~19.
In XRD diagram as shown in figure 16, sample 1 has apparent peak, spacing d=0.96nm, compared to GO at 9.22 °
The interlamellar spacing of (10.34 °) has slight variation, it may be possible to insert amine between graphene oxide layer, lead to the increase of interlamellar spacing.
In the wavy property that 21.46 ° or so of peak values are modified graphene structure, there is the overlapping of part in partial region, thus also illustrates
It is restored to a certain extent by aminated graphene.In addition, the XRD spectrum for comparing different TAPA additive amounts can
With discovery, with the increase of TAPA amount, the interlamellar spacing of graphene is in the trend increased, this is because TAPA is in graphene sheet layer
Play the role of space obstacle, to play sulfur fixation, improves the capacity retention ratio of lithium-sulfur cell.
As shown in Figure 17~19, Figure 17 GO-TAPA3.1mmol(sample 1), Figure 18 GO-TAPA2.06mmol(sample 2) and
Figure 19 is GO-TAPA1.03mmolThe scanning electron microscope (SEM) photograph of (sample 3).With the increase of TAPA amount, graphene surface degree of roughness increases
Add.This is because barrier action is stronger, simultaneously as a large amount of eliminations of oxygen-containing functional group, graphene layer when TAPA dosage increases
Fault of construction increases, so that surface is more coarse, this plays certain positive effect to captured sulfur result, thus improves lithium sulphur electricity
The capacity retention ratio in pond.
Sample 1,4 and 5 performance evaluations
Sample 1, sample 4 and sample 5 are compared and analyzed by X-ray diffraction analysis (XRD), concrete outcome is shown in Figure 20.
As shown in figure 20, it can see in the identical situation of additive amount, compared to three (4- aminophenyl) amine (sample 1)
With 1,3,5- tri- (4- aminophenyl) benzene (sample 5) have adulterated the graphene layer spacing of three (2- amino-ethyl) amine (sample 4)
Reduce.This may be because three (2- amino-ethyl) amine have certain flexibility, and have the three of the benzene ring structure of certain rigidity
(4- aminophenyl) benzene and 1,3,5- tri- (4- aminophenyl) benzene can support the space structure of graphene oxide, therefore interlamellar spacing
Slightly increased.
Claims (9)
1. a kind of preparation method of nitrogen-doped graphene material, which comprises the following steps:
(1) graphene oxide is dispersed in polar solvent and obtains dispersion liquid；
(2) then stirring plus alkali adjust pH >=9；
(3) nitrogen-doping compound and condensing agent is added in the reaction system obtained by step (2), is stirred to react a period of time
Afterwards, it cleans, is drying to obtain nitrogen-doped graphene material.
2. the preparation method of nitrogen-doped graphene material according to claim 1, which is characterized in that the nitrogen-doping
Compound is three aminated compounds.
3. the preparation method of nitrogen-doped graphene material according to claim 2, which is characterized in that the three amines chemical combination
Object is three (2- amino-ethyl) amine, three (4- aminophenyl) amine or 1,3,5- tri- (4- aminophenyl) benzene.
4. the preparation method of nitrogen-doped graphene material according to claim 1, which is characterized in that the condensing agent is two
The mixture of carbodicyclo hexylimide and I-hydroxybenzotriazole.
5. the preparation method of nitrogen-doped graphene material according to claim 4, which is characterized in that two in the condensing agent
The molar ratio of carbodicyclo hexylimide and I-hydroxybenzotriazole is 1:1.
6. the preparation method of any nitrogen-doped graphene material according to claim 1~5, which is characterized in that the alkali
For sodium hydroxide, the mass ratio of sodium hydroxide and graphene oxide is 1:1, sodium hydroxide, condensing agent and nitrogen-doping chemical combination
The molar ratio of object is 7.5:(6.0~6.5): (1.0~3.5).
7. the preparation method of nitrogen-doped graphene material according to claim 6, which is characterized in that in step (3), reaction
15~30 DEG C of temperature, the reaction time 24 hours, cleaning process used polar solvent and water alternately to clean at least twice respectively, 60 DEG C~
It is dried in vacuo 36~48 hours at 80 DEG C.
8. the preparation method of nitrogen-doped graphene material according to claim 7, which is characterized in that described in step (1)
Polar solvent is n,N-Dimethylformamide or dimethyl sulfoxide, and dispersion process is that ultrasonic disperse mixes 30~45 minutes.
9. the preparation method of nitrogen-doped graphene material according to claim 8, which is characterized in that in step (2), stirring
15~30 DEG C of temperature, mixing time 1 hour, pH was 11~12.
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