CN107226466A - The method that nitrogen-doped graphene aeroge is prepared using plant extraction liquid modification - Google Patents
The method that nitrogen-doped graphene aeroge is prepared using plant extraction liquid modification Download PDFInfo
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Abstract
The invention discloses a kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, including:1~10 parts by volume graphene oxide solution, 0.5~12 parts by volume nitrogen source and 1~30 parts by volume plant extraction liquid are taken, is stirred, ultrasonic disperse obtains mixed liquor;Mixed liquor is moved in autoclave, in the case where temperature is 80~200 DEG C, 12~20h is reacted, obtains hydrogel;By hydrogel after dialysis 1~12h of precooling at 0~20 DEG C, after taking-up spontaneously dry, that is, obtain nitrogen-doped graphene aeroge.Using the present invention, the graphene aerogel of preparation has high N doping amount, laid the foundation for the functional material for preparing various nitrogen-doped graphene bases, available for preparing the fields such as various microswitches, jogging sensor and ultracapacitor, lithium battery, solar cell, refractory material, catalysis material, sorbing material, oil absorption material.Preparation method operating procedure of the present invention is easy, easy to operate, can realize large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of graphene aerogel, and in particular to one kind is modified system using plant extraction liquid
The method of standby nitrogen-doped graphene aeroge.
Background technology
Graphene unique electricity, calorifics and mechanical property make it be deposited in electronic device, composite, sensor, energy
The fields such as storage have broad application prospects.It is all it is known due to, the electric conductivity of graphene can not be controlled completely because
It does not have band gap.The doping of graphene is by using including N, B, P, and S etc. hetero atom substitution carbon atom forms point defect with this
Open its band gap and modulation conduction type.Therefore graphene element doping have become the upsurge studied now in recent years by
Substantial amounts of document is reported.And the N doping of graphene is as most common doping way, it has been prepared for various mixing based on nitrogen
Miscellaneous functional graphene material.It is known that there is big electronegativity between N atoms and C atoms, this can increase C atom adjacent
On charge density, so as to improve chemical property.And there are some researches show the doping of N element not only increases graphite
Interaction between alkene and nano material, and the avtive spot of grappling metal nanoparticle is added, to further enhance
Its catalytic activity.So the graphene-based material of N doping has broad application prospects.Based on this, nitrogen-doped graphene material
Preparation of industrialization we should more pay attention in again.At present, preparing the method for nitrogen-doped graphene aeroge mainly has in situ from group
Assembling of dress, chemical crosslinking, chemical vapor deposition (CVD), electrochemistry formated, and template mediation etc..But in these methods,
Mostly research energy stores/conversion, molecular hybrid thing/compound, the allotrope of carbon structure transformation, but no matter
Application in terms of which we all it is seen that, wherein most preparation method be required for it is dry using freeze-drying or vacuum
Dry, this needs expensive instrument, the cost of great number, limited yield;And most of used reducing agent is chemical reagent,
This not only can cause severe contamination also to influence its industrialized production on environment.To sum up all the reason for are just heavy industrialization
Volume production doped graphene brings inconvenience.
In the present invention, we use the fragrant plant extraction liquid of pure natural left hand to be made as modifying agent under natural drying
Standby nitrogen mixes graphene aerogel.This is the mode of production with extremely strong competitiveness, because using the fragrant plant extraction liquid of left hand for also
Former agent will not be polluted to environment, while spontaneously drying with low cost, easy processing, not needing high equipment and without dirt
The advantages of dye.Nevertheless, the nitrogen under spontaneously drying mixes graphene aerogel structure generally built on the sand, serious shape is easily caused
Shape is deformed.Strengthens intercellular structure using boric acid as being previously reported by, in higher plant body, this can with sclereid wall,
Improve the support strength between cell membrane, although had what work sutdy boric acid was prepared to graphene film and graphene aerogel
Influence, but regrettably, not directly using plant extraction liquid is this more environmentally-friendly and mode of suitable volume production
Graphene aerogel is prepared, so we directly strengthen nitrogen using plant extraction liquid mixes cross-bridge between graphene aerogel
Effect is connect, makes it have enough intensity to resist the shape distortion produced during natural drying.
The preparation method of the present invention is only using a certain amount of ammoniacal liquor, urea as nitrogen source, with the fragrant plant extract of a certain amount of left hand
Liquid prepares the graphene airsetting for the high nitrogen doped amount that can be spontaneously dried by hydro-thermal method plant extraction liquid as modifying agent
Glue, is that reducing agent will not be polluted to environment using the fragrant plant extraction liquid of left hand, while spontaneously drying with low cost, Yi Jia
Work, the advantages of do not need high equipment and be pollution-free, and preparation process of the present invention is simple, and cost is low, efficiently, no dirt
Dye.
The content of the invention
It is contemplated that overcoming the shortcoming of existing method, the preparation method in the present invention is only made with a certain amount of ammoniacal liquor, urea
For nitrogen source, the fragrant plant extraction liquid of a certain amount of left hand is as modifying agent, and being prepared by hydro-thermal method plant extraction liquid can be natural
The graphene aerogel of dry high nitrogen doped amount, simplifies existing preparation process, efficiently, pollution-free, with outstanding elasticity,
Electrochemistry, oil absorbing and fire resistance.Available for prepare various microswitches, jogging sensor and ultracapacitor, lithium electricity
The fields such as pond, solar cell, refractory material, catalysis material, sorbing material, oil absorption material.
It is an object of the invention to solve at least the above and/or defect, and provide at least will be described later excellent
Point.
Changed to realize according to object of the present invention and further advantage there is provided a kind of using plant extraction liquid
The method that property prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: taking 1~10 parts by volume graphene oxide solution, 0.5~12 parts by volume nitrogen source and 1~30 parts by volume plant
Extract solution, stirring, ultrasonic disperse obtains mixed liquor;
Step 2: mixed liquor is moved in autoclave, in the case where temperature is 80~200 DEG C, 12~20h is reacted, is obtained
To hydrogel;
Step 3: by hydrogel after dialysis 1~12h of precooling at 0~-20 DEG C, after taking-up spontaneously dry, that is, obtain
Nitrogen-doped graphene aeroge.
Preferably, the concentration of the graphene oxide solution is 1~20mg/mL;The concentration of the plant extraction liquid is
0.1~10g/mL.
Preferably, the nitrogen source is one or more combinations in ammoniacal liquor, urea, organic amine material;It is described to have
Machine amine substance is ethylenediamine, diethylamine, isopropylamine, tripropyl amine (TPA), triethanolamine, hexamethylene diamine, acrylamide, dimethylformamide
In one or more of combinations.
Preferably, the nitrogen source is the combination of 1~10 parts by volume ammoniacal liquor and 0.001~0.1 parts by weight of urea.
Preferably, the ethanol water that the dialyzate used of dialysing is 0.1%~10% for concentration, dialysis time
For 1~10h.
Preferably, the plant extraction liquid is with the plant for having reproducibility, crosslinking effect to graphene oxide
Extract solution.
Preferably, the plant extraction liquid is the fragrant extract solution of left hand, radix scutellariae extract solution, Chinese yam extract, radix glycyrrhizae extraction
Liquid, onions extracting liquid, dandelion extract solution, peppermint, which are planted, takes liquid, orange peel extract solution, Herba Houttuyniae extract, gingko extract solution, the bighead atractylodes rhizome
One or more of combinations in extract solution.
Preferably, the process of the step one is replaced with:Take 1~10 parts by volume graphene oxide solution, 0.5~12 body
Product part nitrogen source and 1~30 parts by volume plant extraction liquid, add in stainless steel spherical container, spherical container are placed in into four axle bevellers
On, four axle bevellers are opened, drive stainless steel spherical container randomly to rotate, 30~60min are reacted, then ultrasonic disperse, is obtained
Mixed liquor;The charging aperture of the stainless steel spherical container is sealed by threaded cap, and threaded cap is tightly connected rear and stainless steel ball
Describe that the surface of device is flushed;The rotating shaft rotating speed of the four axles beveller is 100~150rpm, and stochastic transition frequency is 30~60s.
Preferably, the process of the step 2 is replaced with:Mixed liquor is added in supercritical reaction apparatus, then will
System is sealed, and is reacted 6~12 hours under conditions of being passed through at carbon dioxide to 15~25MPa, 80~200 DEG C of temperature.
Preferably, the ultrasonic power regulating range is in 500~1000W, and supersonic frequency is in 25~50KHz.
Heretofore described graphene oxide solution includes being prepared by Hummer ' s methods, is dissolved in by graphene oxide solid
Water preparation etc..
In step 3 of the present invention, precooling purpose is can to make the moisture formation ice crystal in graphene hydrogel;Naturally do
Dry is at normal temperatures and pressures, the moisture evaporation in hydrogel is become the process of aeroge.
In the present invention, because the effect of the fragrant extract solution mesoboric acid salt of left hand can make graphene oxide carry out crosslinking bridge,
It is set to be self-assembled into hydrogel;And can be to the oxygen-containing function on graphene oxide sheet containing polynary polysaccharide polyol in the fragrant extract solution of left hand
Group is reduced, and this causes a large amount of reductions of oxy radical;And urea then can with ammoniacal liquor in water-heat process together as nitrogen source
N atoms are enable to be entrained in graphene oxide.
The present invention at least includes following beneficial effect:
(1) using the present invention, only using a certain amount of ammoniacal liquor, urea as nitrogen source, the fragrant plant extraction liquid of a certain amount of left hand is made
For modifying agent, the graphene aerogel for the high nitrogen doped amount that can be spontaneously dried is prepared by hydro-thermal method plant extraction liquid.
(2) using the present invention, preparation process is simply efficient, non-environmental-pollution, with outstanding elasticity, electrochemistry, oil
Absorbability and fire resistance.
(3) using the present invention, the graphene aerogel of preparation has high N doping amount, to prepare various N doping graphite
The functional material of alkenyl lays the foundation, available for prepare various microswitches, jogging sensor and ultracapacitor, lithium battery,
The fields such as solar cell, refractory material, catalysis material, sorbing material, oil absorption material.
(4) preparation method operating procedure of the present invention is easy, easy to operate, can realize large-scale production.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings:
Fig. 1 shows the volume before and after the drying of nitrogen-doped graphene aeroge prepared by embodiment 1~4 and comparative example 1
Conservation rate curve map;
Fig. 2 is the SEM figures for the nitrogen-doped graphene aeroge that the embodiment of the present invention 1 is prepared;
Fig. 3 shows that the nitrogen-doped graphene aeroge that embodiment 1 is prepared sweeps specific capacitances and appearance under speed in difference
Measure conservation rate;
Fig. 4 is the nitrogen-doped graphene aeroge prepared in the embodiment of the present invention 1 as electrode material for super capacitor
Constant current charge-discharge curve.
Fig. 5 shows the elasticity performance test figure of nitrogen-doped graphene aeroge prepared by embodiment 1~3 and comparative example 1;
Fig. 6 is x-ray photoelectron power spectrum (XPS) figure of nitrogen-doped graphene aeroge prepared by embodiment 1.
Embodiment:
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or many
The presence or addition of individual other elements or its combination.
Embodiment 1:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: take 6mL 10mg/L graphene oxide solution and 4mL concentrated ammonia liquors stirring, then add 60mg urea and
The fragrant plant extraction liquid of 3mL 0.3g/mL left hand, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is
800W, supersonic frequency is in 35KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 180 DEG C, instead
12h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 12h at -17 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 1% for concentration, dialysis time is 6h.
Fig. 2 (a-f) shows the SEM figures for the nitrogen-doped graphene aeroge that embodiment 1 is prepared;Can from figure
Going out nitrogen-doped graphene aeroge has the layered porous skeletons of equally distributed 3D, and this can greatly reduce capillary force.
Fig. 3 shows that the nitrogen-doped graphene aeroge that embodiment 1 is prepared sweeps specific capacitances and appearance under speed in difference
Measure conservation rate, the specific capacitance under 1A/g reaches 371F/g, this is already higher than many common reports, it is presumed that this be by
Because the fragrant plant extraction liquid of left hand substantially reduces the oxygen-containing functional group of graphene after hydro-thermal, enable N atoms it is easier enter
Enter carbon atomic layer formation carbonnitrogen bond.Meanwhile, sample is under 20A/g current density, and specific capacitance still has 259F/g;It is prior
It is that we also have detected the high rate performance of sample under up to 50A/g high current density, its specific capacitance remains to reach 204F/
G, with about 54.987% capability retention, shows the high rate performance of brilliance.
Fig. 4 is the nitrogen-doped graphene aeroge prepared in the embodiment of the present invention 1 as electrode material for super capacitor
Discharge and recharge specific capacitance figure, under 20A/g current density, nitrogen-doped graphene aeroge first discharge specific capacity is 259F/g,
After 10000 times circulate, specific capacitance remains to be maintained at 245F/g.
Fig. 6 is x-ray photoelectron power spectrum (XPS) figure of nitrogen-doped graphene aeroge prepared by embodiment 1.From Fig. 6 a
Find out, in nitrogen-doped graphene aeroge N doping be 12.06%, Fig. 6 b in show the nitrogen-doped graphene that will be obtained
Aeroge sample obtains three kinds of different compositions by carrying out peak-fit processing to N 1s peaks, it means that N atoms are in bonding graphite
There are three kinds of different valence states, respectively pyridine N (Pyridinic-N 398.7eV ± 0.2), pyrroles N (Pyrrolic-N during alkene
399.3eV ± 0.2), graphite N (Graphitic/quaternary-N 401.4 ± 0.3).
Embodiment 2:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: take 6mL 10mg/L graphene oxide solution and 4mL concentrated ammonia liquors stirring, then add 60mg urea and
The fragrant plant extraction liquid of 1mL 0.3g/mL left hand, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is
800W, supersonic frequency is in 35KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 180 DEG C, instead
12h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 12h at -17 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 1% for concentration, dialysis time is 6h.
Embodiment 3:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: take 4mL 10mg/L graphene oxide solution and 4mL concentrated ammonia liquors stirring, then add 60mg urea and
The fragrant plant extraction liquid of 5mL 0.3g/mL left hand, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is
800W, supersonic frequency is in 35KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 180 DEG C, instead
12h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 12h at -17 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 5% for concentration, dialysis time is 6h.
Embodiment 4:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: taking 4mL 1mg/L graphene oxide solution and the stirring of 4mL concentrated ammonia liquors, 60mg urea is then added, is stirred
Mix, ultrasonic disperse obtains mixed liquor;The ultrasonic power is 800W, and supersonic frequency is in 35KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 180 DEG C, instead
12h is answered, hydrogel is obtained;
Step 3: directly freezed is dried after dialysis by hydrogel, that is, obtain nitrogen-doped graphene aeroge;It is described
The ethanol water that the dialyzate used is 1% for concentration is analysed, dialysis time is 6h.
Comparative example 1:
In preparation process, be not added with the fragrant plant extraction liquid of left hand, its with technical process and parameter with it is complete in embodiment 1
It is exactly the same.
Fig. 1 shows the volume before and after the drying of nitrogen-doped graphene aeroge prepared by embodiment 1~4 and comparative example 4
Conservation rate, when carrying out directly freezed drying to sample (embodiment 4), it has about 97.879% volume conservation rate, in nature
Under drying, when the fragrant plant extraction liquid of left hand is 3mL (embodiment 1), volume conservation rate reaches optimal for 95.643%.And do not add
Added-time (comparative example 1), only 75.274% volume conservation rate.Hair can significantly be resisted by showing the addition of the fragrant plant extraction liquid of left hand
Tubule power, illustrates to use the addition of the fragrant plant extraction liquid of left hand in the present invention and using spontaneously drying, can obtain volume holding
The high nitrogen-doped graphene aeroge of rate, Fig. 1 illustration photo shows in embodiment 1 that nitrogen-doped graphene aeroge is natural
Volume Changes before and after drying.
The loading and unloading of nitrogen-doped graphene aeroge sample prepared by embodiment 1~3 and comparative example 1 in 5mm/min
Mechanics Performance Testing is carried out under speed.If Fig. 5 a are fragrant plant extraction liquid (PAPE) consumption (comparative example 1 of different left hands:0mL;It is real
Apply example 1:3mL;Embodiment 2:1mL;Embodiment 3:Nitrogen-doped graphene aeroge sample 5mL) respectively 55%, 85% and
Stress-strain diagram under 95% strain, although sample can show great dependent variable (95%), but the maximum of sample
Compression has larger difference (the maximum crushing stress fluctuation that 78~180MPa is shown as under being strained 95%).It is in PAPE consumptions
During 3mL (embodiment 1), stress reaches 180KPa, and when PAPE consumptions are 1mL (embodiment 2), stress reaches 162KPa, and this makes
Graphene aerogel has enough rigidity to resist the capillary pressure produced when spontaneously drying.Embodiment 1~3 and contrast
The nitrogen-doped graphene aeroge sample of example 1 adds unloading curve as shown in Figure 5 b under 95% strain, in different compression ranks
Section sample shows different deformation mechanisms.Work as ε<When 70%, curve is gentle, now mainly in nitrogen-doped graphene aeroge
Macroporous structure deform, microstructure still keeps stable;When 70%<ε<When 95%, curve shows obvious climbing, this
When finished substantially by compression due to macroporous structure, mainly micropore, it is mesoporous start deformation and graphene film start it is tightly packed,
Macro manifestations increased dramatically for compression stress, and the illustration in Fig. 5 b shows nitrogen-doped graphene airsetting prepared by embodiment 1
The photo of glue one press cycles in 95% plus unloading, illustrates that the nitrogen-doped graphene aeroge has excellent elasticity;Figure
5c show embodiment 1 prepare nitrogen-doped graphene aeroge 55% strain under first 5 times compression circulation, for the first time load
When stress substantially far above other, and the maximum elastance with 11.8KPa illustrate that sample rigidity is enough to resist at oneself
Produced capillary pressure when so drying.After the first second compression more substantially, compression hysteresis loop then is not for hysteresis loop
Substantially, and with the increase of compression number of times it is gradually reduced, illustration therein shows change of the modulus of elasticity with cycle-index
Trend.Fig. 5 d show nitrogen-doped graphene aeroge recoverable strain prepared by embodiment 1 with compression number of times and dependent variable
Variation tendency, has carried out 10 circulations under being strained respectively 55%, 85%, 95%.As fig 5d, after 30 times circulate,
Shrink and reduce, the macroscopic form of nitrogen-doped graphene aeroge as expected except hysteresis loop and maximum crushing stress are produced respectively
Have almost no change, be maintained to original height and it is no rupture, this shows that doped graphene aeroge can be with
In deformation of any stage (less than 95%), it was demonstrated that applied widely, wherein, illustration is relative with cycle-index when showing plus unloading
Change.
Embodiment 5:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: taking 10mL 5mg/L graphene oxide solution and the stirring of 8mL concentrated ammonia liquors, 0.05g urea is then added
With the 10mL 5g/mL fragrant plant extraction liquid of left hand, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is
500W, supersonic frequency is in 25KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 200 DEG C, instead
16h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 12h at -20 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 1% for concentration, dialysis time is 10h.
Embodiment 6:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: take 5mL 15mg/L graphene oxide solution and 6mL concentrated ammonia liquors stirring, then add 0.1g urea and
The fragrant plant extraction liquid of 20mL 20g/mL left hand, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is
500W, supersonic frequency is in 25KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 200 DEG C, instead
16h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 8h at -18 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 10% for concentration, dialysis time is 10h.
Embodiment 7:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: taking 8mL 10mg/L graphene oxide solution and the stirring of 5mL concentrated ammonia liquors, 6mL ethylenediamines are then added
With the 20mL 5g/mL fragrant plant extraction liquid of left hand, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is
500W, supersonic frequency is in 25KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 200 DEG C, instead
16h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 8h at -15 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 10% for concentration, dialysis time is 10h.
Embodiment 8:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: taking 6mL 20mg/L graphene oxide solution and the stirring of 8mL concentrated ammonia liquors, the ethanol of 1mL tri- is then added
The fragrant plant extraction liquid of amine and 20mL 3g/mL left hand, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is
500W, supersonic frequency is in 25KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 200 DEG C, instead
16h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 12h at -10 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 5% for concentration, dialysis time is 10h.
Embodiment 9:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: taking 6mL 20mg/L graphene oxide solution and the stirring of 4mL concentrated ammonia liquors, 4mL acryloyls are then added
The licorice extract of amine and 30mL 8g/mL, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is 500W, is surpassed
Acoustic frequency is in 25KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 180 DEG C, instead
16h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 12h at -10 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 5% for concentration, dialysis time is 10h.
Embodiment 10:
A kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, comprises the following steps:
Step 1: taking 10mL 15mg/L graphene oxide solution and the stirring of 6mL concentrated ammonia liquors, 2mL acryloyls are then added
The orange peel extract solution of amine and 20mL 10g/mL, stirring, ultrasonic disperse obtains mixed liquor;The ultrasonic power is 500W,
Supersonic frequency is in 25KHz;
Step 2: mixed liquor is moved in the autoclave containing Teflon liner, in the case where temperature is 200 DEG C, instead
16h is answered, hydrogel is obtained;
Step 3: by hydrogel after dialysis the precooling 12h at -10 DEG C, after taking-up spontaneously dry, that is, obtain N doping
Graphene aerogel;The ethanol water that the dialyzate used of dialysing is 5% for concentration, dialysis time is 10h.
Embodiment 11:
The process of the step one is replaced with:Take 6mL 10mg/L graphene oxide solution, 4mL concentrated ammonia liquors to stir,
The fragrant plant extraction liquid of 60mg urea and 3mL 0.3g/mL left hand, adds in stainless steel spherical container, spherical container is placed in into four
On axle beveller, four axle bevellers are opened, drive stainless steel spherical container randomly to rotate, 60min are reacted, then ultrasonic disperse,
Obtain mixed liquor;The charging aperture of the stainless steel spherical container is sealed by threaded cap, threaded cap be tightly connected after with it is stainless
The surface of steel ball shape container is flushed;The rotating shaft rotating speed of the four axles beveller is 120rpm, and stochastic transition frequency is 60s.Remaining
Technological parameter and process with it is identical in embodiment 1.The present invention carries spherical container by four axle bevellers, realizes spherical
Random rotation solidification in container.Sealing spherical container is fixed by four support shafts of four axle bevellers, adjusted
Change-over period between four axle slewing rates and active and driven shaft, realize the trackless orientation in additional flow field.Pass through this method
Random rotation hybrid reaction, makes the modified-reaction of plant extraction liquid and graphene oxide more complete.
Nitrogen-doped graphene aeroge prepared by embodiment 11 carries out performance test:Drying front and rear volume conservation rate is
97.125%;Under 20A/g current density, first discharge specific capacity is 269F/g, after 10000 times circulate, specific capacitance
Amount remains to be maintained at 260F/g;In the case where 95% strains, maximum stress reaches 188KPa.
Embodiment 12:
The process of the step one is replaced with:Take 6mL 10mg/L graphene oxide solution, 4mL concentrated ammonia liquors to stir,
The fragrant plant extraction liquid of 60mg urea and 1mL 0.3g/mL left hand, adds in stainless steel spherical container, spherical container is placed in into four
On axle beveller, four axle bevellers are opened, drive stainless steel spherical container randomly to rotate, 45min are reacted, then ultrasonic disperse,
Obtain mixed liquor;The charging aperture of the stainless steel spherical container is sealed by threaded cap, threaded cap be tightly connected after with it is stainless
The surface of steel ball shape container is flushed;The rotating shaft rotating speed of the four axles beveller is 150rpm, and stochastic transition frequency is 30s.Remaining
Technological parameter and process with it is identical in embodiment 2.
Nitrogen-doped graphene aeroge prepared by embodiment 12 carries out performance test:Drying front and rear volume conservation rate is
95.712%;In the case where 95% strains, maximum stress reaches 175KPa.
Embodiment 13:
The process of the step 2 is replaced with:Mixed liquor is added in supercritical reaction apparatus, then system is sealed,
Reacted 8 hours under conditions of being passed through at carbon dioxide to 20MPa, 150 DEG C of temperature.Remaining technological parameter and process and embodiment 1
In it is identical.
Nitrogen-doped graphene aeroge prepared by embodiment 13 carries out performance test:Drying front and rear volume conservation rate is
97.855%;Under 20A/g current density, first discharge specific capacity is 268F/g, after 10000 times circulate, specific capacitance
Amount remains to be maintained at 259.5F/g;In the case where 95% strains, maximum stress reaches 187KPa.
Embodiment 14:
The process of the step 2 is replaced with:Mixed liquor is added in supercritical reaction apparatus, then system is sealed,
Reacted 10 hours under conditions of being passed through at carbon dioxide to 25MPa, 160 DEG C of temperature.Remaining technological parameter and process and embodiment 2
In it is identical.
Nitrogen-doped graphene aeroge prepared by embodiment 14 carries out performance test:Drying front and rear volume conservation rate is
96.515%;In the case where 95% strains, maximum stress reaches 176KPa.
Embodiment 15:
The process of the step 2 is replaced with:Mixed liquor is added in supercritical reaction apparatus, then system is sealed,
Reacted 10 hours under conditions of being passed through at carbon dioxide to 25MPa, 160 DEG C of temperature.Remaining technological parameter and process and embodiment
It is identical in 11.
Nitrogen-doped graphene aeroge prepared by embodiment 15 carries out performance test:Drying front and rear volume conservation rate is
98.225%;Under 20A/g current density, first discharge specific capacity is 275F/g, after 10000 times circulate, specific capacitance
Amount remains to be maintained at 268F/g;In the case where 95% strains, maximum stress reaches 190KPa.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the legend with description.
Claims (10)
1. a kind of method that utilization plant extraction liquid modification prepares nitrogen-doped graphene aeroge, it is characterised in that including following
Step:
Step 1: taking 1~10 parts by volume graphene oxide solution, 0.5~12 parts by volume nitrogen source and 1~30 parts by volume plant extract
Liquid, stirring, ultrasonic disperse obtains mixed liquor;
Step 2: mixed liquor is moved in autoclave, in the case where temperature is 80~200 DEG C, 12~20h is reacted, water is obtained
Gel;
Step 3: by hydrogel after dialysis 1~12h of precooling at 0~-20 DEG C, after taking-up spontaneously dry, that is, obtain nitrogen and mix
Miscellaneous graphene aerogel.
2. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In the concentration of the graphene oxide solution is 1~20mg/mL;The concentration of the plant extraction liquid is 0.1~10g/mL.
3. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In the nitrogen source is one or more combinations in ammoniacal liquor, urea, organic amine material;The organic amine material is second
One or more in diamines, diethylamine, isopropylamine, tripropyl amine (TPA), triethanolamine, hexamethylene diamine, acrylamide, dimethylformamide
Combination.
4. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In the nitrogen source is the combination of 1~10 parts by volume ammoniacal liquor and 0.001~0.1 parts by weight of urea.
5. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In, the ethanol water that the dialyzate used of dialysing is 0.1%~10% for concentration, dialysis time is 1~10h.
6. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In the plant extraction liquid is with the plant extraction liquid for having reproducibility, crosslinking effect to graphene oxide.
7. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 6, its feature exists
In, the plant extraction liquid be the fragrant extract solution of left hand, radix scutellariae extract solution, Chinese yam extract, licorice extract, onions extracting liquid,
Dandelion extract solution, peppermint plant the one kind taken in liquid, orange peel extract solution, Herba Houttuyniae extract, gingko extract solution, bighead atractylodes rhizome extract solution
Or several combinations.
8. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In the process of the step one is replaced with:Take 1~10 parts by volume graphene oxide solution, 0.5~60 parts by volume nitrogen source and 1~
30 parts by volume plant extraction liquids, add in stainless steel spherical container, spherical container are placed on four axle bevellers, open four axles and grind
Instrument is ground, drives stainless steel spherical container randomly to rotate, 30~60min is reacted, then ultrasonic disperse, obtains mixed liquor;It is described
The charging aperture of stainless steel spherical container is sealed by threaded cap, and the surface that threaded cap is tightly connected afterwards with stainless steel spherical container is neat
It is flat;The rotating shaft rotating speed of the four axles beveller is 100~150rpm, and stochastic transition frequency is 30~60s.
9. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In the process of the step 2 is replaced with:Mixed liquor is added in supercritical reaction apparatus, then system is sealed, is passed through
Reacted 6~12 hours under conditions of at carbon dioxide to 15~25MPa, 80~200 DEG C of temperature.
10. the method for preparing nitrogen-doped graphene aeroge using plant extraction liquid modification as claimed in claim 1, its feature exists
In the ultrasonic power regulating range is in 500~1000W, and supersonic frequency is in 25~50KHz.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
CN104174424A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of nitrogen-doped graphene aerogel supported non-precious metal oxygen reduction catalyst |
CN106006615A (en) * | 2016-05-25 | 2016-10-12 | 哈尔滨工业大学 | Natural drying preparation method of graphene aerogel |
-
2017
- 2017-08-01 CN CN201710645216.7A patent/CN107226466B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
CN104174424A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of nitrogen-doped graphene aerogel supported non-precious metal oxygen reduction catalyst |
CN106006615A (en) * | 2016-05-25 | 2016-10-12 | 哈尔滨工业大学 | Natural drying preparation method of graphene aerogel |
Non-Patent Citations (1)
Title |
---|
PRAJWAL CHETTRI ET AL.,: "Self assembly of functionalised graphene nanostructures by one step reduction vulgaris", 《APPLIED SURFACE SCIENCE》 * |
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