CN106542522B - The method that template prepares three-dimensional grapheme - Google Patents
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Abstract
The method that template prepares three-dimensional grapheme, it is related to a kind of method that template prepares three-dimensional grapheme.The present invention is to solve the technical problems of high cost, complicated for operation for preparing three-dimensional porous nitrogen-doped graphene.This method：One, dispersion liquid is prepared；Two, dust technology, dilute sulfuric acid or phosphoric acid are added in dispersion liquid obtained by step 1, are precipitated；Three, products therefrom will be filtered to be re-dispersed into mold of different shapes with ethyl alcohol, it is dry, obtain presoma；Four, presoma is heated up and is kept the temperature under conditions of argon gas or nitrogen, then heating and heat preservation is to get three-dimensional grapheme.The present invention is raw material using cheap melamine or dicyandiamide, the three-dimensional grapheme prepared is about 10 yuan/g, far below the price (market price of graphene is about 100 1000 yuan/g at present) of presently commercially available graphene, it is suitble to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of methods preparing three-dimensional grapheme.
Background technology
Grapheme material is a kind of monoatomic layer material with unique bi-dimensional cellular shape structure, is to constitute fowler
The basic structural unit of alkene, carbon nanotube and graphite.Graphene has excellent electricity, calorifics and mechanical property, can be extensive
Applied to fields such as the energy, environment and biologies, graphene further can be further expanded by adulterating exotic atom (such as N, S, P etc.)
Application.But since graphene sheet layer is easy to agglomerate into the lower two-dimensional structure material of porosity, in order to further send out
The potential of graphene-based material is waved, three-dimensional porous nitrogen-doped graphene receives more and more attention.(Cao,et
al.small.,2011,7,3163；Hu,et al.Adv.Mater.,2013,25,2219).Three-dimensional porous nitrogen-doped graphene
There are many more other excellent properties other than the physico-chemical property with graphene itself, such as 1, its unique three-dimensional hole knot
Structure has the function of supporting and alleviating internal stress, can be used for the fields such as lithium ion battery, sodium-ion battery, Magnesium ion battery,
Volume expansion and contraction of the negative material in charge and discharge process can be effectively relieved；2, inner void height is connected to, and is conducive to heat conduction
And conduction, it can be used for the fields such as Heat Conduction Material, fuel cell and solar cell；3, its hole has capillary absorption power, can be with
For fields such as pollutant removal, water-oil separatings, further, be conducive to its hole adsorption capacity, be conducive to electrolyte diffusion and
Absorption, has wider application in energy storage fields such as lithium ion, sodium ion, aluminium ion batteries.
Currently, the preparation method of three-dimensional porous nitrogen-doped graphene is mainly the following：1, self-assembly method (Cong, et
al.ACS Nano.,2012,6,2693；Tang, et al.J.Am.Chem.Soc., 2011,133,9262), the method is general
Need that the organic matters such as crosslinking agent are added from graphene oxide and in preparation process, inside high-temperature high-pressure reaction kettle into
Row cross-linking reaction reduces the electrically and thermally property of graphene, limits its further practical application；2, template
(Cheng, et al.Nat.Mater., 2011,10,424；Cao.et al.Small., 2013,9,1703.), this three dimensional network
Network body material has the unique shape characteristic of three-dimensional network and the unique physicochemical properties of graphene, higher porosity and very
Big specific surface area, but it be the expensive metals such as copper, nickel, cobalt is template that its is template used, and the later stage needs to perform etching template, from
The application of its large-scale commercial is limited in terms of economy and environment.Therefore, it is difficult that extensive preparation is cheap high performance at present
Three-dimensional porous structure nitrogen-doped graphene.
Invention content
The present invention is for the more expensive technology of the three-dimensional porous structure nitrogen-doped graphene for solving existing method preparation
Problem provides a kind of method that template prepares three-dimensional grapheme.
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 5-500mg graphene oxides and 2.5-50g melamines or dicyandiamide ultrasonic disperse to 0.2-2L solvents
In, obtain dispersion liquid；
Two, dispersion liquid obtained by step 1 is added in the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 0.1-2mol/L of 0.05-1L
In, it is precipitated；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into not similar shape with ethyl alcohol
In the mold of shape, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised under conditions of argon gas or nitrogen with the heating rate of 1-2 DEG C/min
300-400 DEG C and keep the temperature 2 hours, then with the heating rate of 1-5 DEG C/min be increased to 750-900 DEG C and keep the temperature 2 hours to get three
Tie up graphene.
Solvent described in step 1 is ethylene glycol, water or ethyl alcohol.
The present invention method be：Using melamine or dicyandiamide fiber is formed under the action of nitric acid, sulfuric acid or phosphoric acid
As template, the surface that graphene oxide self assembly is wrapped in fiber constitutes presoma, and the presoma is in high-temperature heat treatment, and three
Poly cyanamid or dicyandiamide filament contraction are decomposed, and outer oxide graphene is reduced, and finally obtains the three-dimensional porous graphite of N doping
Alkene skeleton structure.In addition, also preparing the three-dimensional porous N doping skeleton of different geometric shapes using different molds.The present invention's
Method is simple, and inexpensively, there is gained special construction and the three-dimensional porous graphene of shape can effectively improve the available of graphene
Load area, prepared three-dimensional porous graphene can be widely used for lithium ion battery, fuel cell, ultracapacitor, light and urge
The fields such as change, catalysis oxidation, gas sensor, flexible energy storage device.
Three-dimensional porous nitrogen-doped graphene prepared by the above method can be of different shapes, can be used for various flexible
In the energy storage device that special shape requires, such as flexible super capacitor and flexible lithium ion battery field；Three-dimensional grapheme can
With with titanium dioxide (TiO2), stannic oxide (SnO2), ferroso-ferric oxide (Fe3O4), cobalt oxide (CoO), manganese oxide (MnO2), oxygen
Change copper (CuO), molybdenum sulfide (MoS2), gold nanoparticle (Au), nano platinum particle (Pt) or Pd nano particle (Pd) is compound obtains
The graphene composite material of three-dimensional porous structure is simultaneously applied to lithium ion battery, fuel cell, ultracapacitor, photocatalysis, urges
Change oxidation, gas sensor domain.
The present invention includes following advantageous effect：
1, the present invention wraps up graphene oxide in melamine or dicyandiamide fiber surface by the method for self assembly and constructs
Presoma, using contraction, the decomposition of melamine or dicyandiamide fiber at high temperature, to prepare three-dimensional graphene framework structure；
2, three-dimensional grapheme prepared by the present invention carries out doping in situ using melamine or dicyandiamide, obtains being nitrogen
Adulterate three-dimensional grapheme；
3, the present invention prepared by graphene, can be prepared using variously-shaped mold presoma of different shapes come into
One step prepares the three-dimensional grapheme of different geometric shapes；
4, the present invention is raw material using cheap melamine or dicyandiamide, the three-dimensional grapheme prepared is about 10 yuan/
G is far below the price (market price of graphene is about 100-1000 members/g at present) of presently commercially available graphene, is suitble to extensive
Industrialized production；
5, the three-dimensional porous nitrogen-doped graphene for preparing of the present invention as sodium-ion battery cathode in 200mA g-1Charge and discharge
500 circle capacity of cycle reaches 305mAh g under electric current-1, and in 5A g-1The charge-discharge cycle 8000 of high current is enclosed capacity and is reached
198mAh g-1, coulombic efficiency shows the high current stability of superelevation close to 100%.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture for testing presoma in a step 2；
Fig. 2 is the scanning electron microscopic picture for the three-dimensional grapheme for testing a gained heart shape；
Fig. 3 is the conduct sodium-ion battery for the three-dimensional grapheme for testing a gained heart shape in 200mA g-1Charging and discharging currents
In the case of cycle 500 circle cyclic curve and coulombic efficiency curve.
Specific implementation mode
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary combination.
Specific implementation mode one：The preparation method of present embodiment three-dimensional grapheme is to carry out according to the following steps：
One, by 5-500mg graphene oxides and 2.5-50g melamines or dicyandiamide ultrasonic disperse to 0.2-2L solvents
In, obtain dispersion liquid；
Two, dispersion liquid obtained by step 1 is added in the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 0.1-2mol/L of 0.05-1L
In, it is precipitated；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into not similar shape with ethyl alcohol
In the mold of shape, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised under conditions of argon gas or nitrogen with the heating rate of 1-2 DEG C/min
300-400 DEG C and keep the temperature 2 hours, then with the heating rate of 1-5 DEG C/min be increased to 750-900 DEG C and keep the temperature 2 hours to get three
Tie up graphene.
Specific implementation mode two：The present embodiment is different from the first embodiment in that the solvent described in step 1 is
Ethylene glycol, water or ethyl alcohol.It is other same as the specific embodiment one.
Specific implementation mode three：It will in step 1 unlike one of present embodiment and specific implementation mode one or two
In 200mg graphene oxides and 30g melamines or dicyandiamide ultrasonic disperse to 1L solvents.It is other with specific implementation mode one or
One of two is identical.
Specific implementation mode four：With 1 in step 4 unlike one of present embodiment and specific implementation mode one to three
DEG C/heating rate of min is raised to 310-390 DEG C.It is other identical as one of specific implementation mode one to three.
Specific implementation mode five：In step 4 unlike one of present embodiment and specific implementation mode one to four with
The heating rate of 1.5 DEG C/min is raised to 320-380 DEG C.It is other identical as one of specific implementation mode one to four.
Specific implementation mode six：With 2 in step 4 unlike one of present embodiment and specific implementation mode one to five
DEG C/heating rate of min is raised to 350 DEG C.It is other identical as one of specific implementation mode one to five.
Specific implementation mode seven：In step 4 unlike one of present embodiment and specific implementation mode one to six again with
The heating rate of 1 DEG C/min is increased to 780 DEG C.It is other identical as one of specific implementation mode one to six.
Specific implementation mode eight：In step 4 unlike one of present embodiment and specific implementation mode one to seven again with
The heating rate of 2 DEG C/min is increased to 800 DEG C.It is other identical as one of specific implementation mode one to seven.
Specific implementation mode nine：In step 4 unlike one of present embodiment and specific implementation mode one to eight again with
The heating rate of 3 DEG C/min is increased to 820 DEG C DEG C.It is other identical as one of specific implementation mode one to eight.
Specific implementation mode ten：In step 4 unlike one of present embodiment and specific implementation mode one to nine again with
The heating rate of 4 DEG C/min is increased to 850 DEG C.It is other identical as one of specific implementation mode one to nine.
Using following experimental verifications effect of the present invention：
Experiment one：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 25mg graphene oxides and 2.5g melamines ultrasonic disperse to 0.2L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 0.1mol/L of 0.2L are added in dispersion liquid obtained by step 1, are obtained
To precipitation；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into heart shape with ethyl alcohol
Mold in, in 70 DEG C of dry 10h, obtain presoma；
Four, the presoma obtained by step 3 is raised to 300 under conditions of argon gas or nitrogen with the heating rate of 2 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 800 DEG C with the heating rate of 5 DEG C/min and keep the temperature 2 hours three-dimensional stone to get heart shape
Black alkene.
The scanning electron microscopic picture of prepared presoma is as shown in Figure 1, from fig. 1, it can be seen that graphene oxide is wrapped up to trimerization
Cyanamide surface；The scanning electron microscopic picture of the three-dimensional grapheme of heart shape obtained by this experiment is as shown in Figure 2.
The three-dimensional porous nitrogen-doped graphene skeleton prepared using experiment one does following tests：
Experiment one：Take three-dimensional grapheme, polytetrafluoroethylene (PTFE) and the black (TIMREXKS- of conductive acetylene of heart shape obtained by 100mg
15, TIMCAL, Switzerlan) it is uniformly mixed according to mass ratio 80: 10: 10, it is applied on copper foil and is used as working electrode, 60 DEG C
It is 6 hours dry,；It is to electrode with lithium metal, microporous polypropylene membrane (Celgard 2300) is diaphragm, the sodium perchlorate of 1mol/L
Ethylene carbonate and dimethyl carbonate (volume ratio 1: 1) solution be electrolyte, assemble sodium-ion battery.
The sodium-ion battery of the three-dimensional grapheme assembling of heart shape prepared by this experiment is in 200mA g-1Charging and discharging currents
In the case of cyclic curve it is as shown in Figure 3；It can find out from figure with 3, the three-dimensional grapheme of heart shape exists as sodium-ion battery cathode
200mA g-1Charging and discharging currents under cycle 500 circle capacity reach 305mAh g-1, coulombic efficiency is close to 100%.
Experiment two：Take the three-dimensional grapheme of heart shape and 500mg SnCl obtained by 80mg4Particle is ultrasonic in 40ml ethyl alcohol
Mixed solution is sealed in water heating kettle and reacts 16 hours for 120 DEG C, drying is washed with deionized in products therefrom, is obtained by 30min
To three-dimensional porous SnO2/ graphene composite material；By the three-dimensional porous SnO of gained2/ graphene composite material, polytetrafluoroethylene (PTFE)
It is uniformly mixed, is applied to according to mass ratio 80: 10: 10 with conductive acetylene black (TIMREXKS-15, TIMCAL, Switzerlan)
The two sides of nickel screen is as working electrode, and 60 DEG C of dryings 6 hours, tabletting is simultaneously 24 hours dry at 120 DEG C；It is to electricity with lithium metal
Pole, microporous polypropylene membrane (Celgard 2300) are diaphragm, the LiPF of 1mol/L6Ethylene carbonate and diethyl carbonate (body
Product ratio 1: 1) solution is electrolyte, assembles lithium ion battery.
Specific capacity is 740mAh/g when gained battery is discharged with 0.1C.
Experiment three：Take the three-dimensional grapheme of heart shape and 800mg FeCl obtained by 50mg3It is ultrasonic in 40ml deionized waters
Mixed solution is sealed in water heating kettle and reacts 10 hours for 150 DEG C, drying is washed with deionized in products therefrom, is obtained by 30min
To three-dimensional porous Fe2O3/ graphene composite material；By the three-dimensional porous Fe of gained2O3/ graphene composite material, polytetrafluoroethyl-ne
Alkene and conductive acetylene black (TIMREXKS-15, TIMCAL, Switzerlan) are uniformly mixed according to mass ratio 85: 5: 10, are applied to
The two sides of nickel screen is as working electrode, and 60 DEG C of dryings 6 hours, tabletting is simultaneously 24 hours dry at 120 DEG C；It is to electricity with lithium metal
Pole, microporous polypropylene membrane (Celgard 2300) are diaphragm, the LiPF of 1mol/L6Ethylene carbonate and diethyl carbonate (body
Product ratio 1: 1) solution is electrolyte, assembles lithium ion battery.
Specific capacity is 800mAh/g when gained battery is discharged with 0.1C.
Experiment four：Two cylindrical three-dimensional porous nitrogen-doped graphenes are taken, respectively will under 5MPa pressure with tablet press machine
It, which is depressed on the polyester dacron film of 0.2mm thickness, is used as ultracapacitor working electrode, with conductive silver paste in working electrode both sides
Copper conductor is drawn, with microporous polypropylene membrane (Celgard 3501) for diaphragm, polyvinyl alcohol (the molecular weight 89000- of the KOH of 6M
98000) dispersion liquid is electrolyte, assembles symmetrical all-solid-state flexible ultracapacitor.
Gained capacity of super capacitor is about 180F g-1。
Experiment two：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 50mg graphene oxides and 2.5g dicyandiamides ultrasonic disperse to 0.2L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 2mol/L of 0.05L are added in dispersion liquid obtained by step 1, are obtained
To precipitation；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into five-pointed star with ethyl alcohol
In the mold of shape, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised under conditions of argon gas or nitrogen with the heating rate of 2 DEG C DEG C/min
300 DEG C and keep the temperature 2 hours, then with the heating rate of 5 DEG C/min be increased to 900 DEG C DEG C and keep the temperature 2 hours to get Five-pointed star
Three-dimensional grapheme.
Experiment three：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 50mg graphene oxides and 5g melamines ultrasonic disperse to 0.5L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 2mol/L of 1L are added in dispersion liquid obtained by step 1, are sunk
It forms sediment；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, will suction filtration products therefrom be re-dispersed into ethyl alcohol it is cylindric
Mold in, in 70 DEG C of dry 10h, obtain presoma；
Four, the presoma obtained by step 3 is raised to 300 under conditions of argon gas or nitrogen with the heating rate of 2 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 900 DEG C with the heating rate of 5 DEG C/min and keep the temperature 2 hours to get columned three-dimensional stone
Black alkene.
Experiment four：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 500mg graphene oxides and 50g dicyandiamides ultrasonic disperse to 0.2-2L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 0.1mol/L of 1L are added in dispersion liquid obtained by step 1, are obtained
Precipitation；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, will suction filtration products therefrom be re-dispersed into ethyl alcohol it is cylindric
Mold in, in 70 DEG C of dry 10h, obtain presoma；
Four, the presoma obtained by step 3 is raised to 300 under conditions of argon gas or nitrogen with the heating rate of 1 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 850 DEG C with the heating rate of 5 DEG C/min and keep the temperature 2 hours to get columned three-dimensional stone
Black alkene.
Experiment five：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 100mg graphene oxides and 50g dicyandiamides ultrasonic disperse to 0.2-2L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 2mol/L of 1L are added in dispersion liquid obtained by step 1, are sunk
It forms sediment；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into five-pointed star with ethyl alcohol
In the mold of shape, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised to 300 under conditions of argon gas or nitrogen with the heating rate of 2 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 900 DEG C with the heating rate of 5 DEG C/min and keep the temperature 2 hours three-dimensionals to get Five-pointed star
Graphene.
Experiment six：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 100mg graphene oxides and 50g melamines ultrasonic disperse to 1L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 2mol/L of 0.05L are added in dispersion liquid obtained by step 1, are obtained
To precipitation；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into five-pointed star with ethyl alcohol
In the mold of shape, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised to 300 under conditions of argon gas or nitrogen with the heating rate of 2 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 800 DEG C with the heating rate of 2 DEG C/min and keep the temperature 2 hours three-dimensionals to get Five-pointed star
Graphene.
Experiment seven：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 100mg graphene oxides and 50g melamines ultrasonic disperse to 0.2-2L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 0.5mol/L of 1L are added in dispersion liquid obtained by step 1, are obtained
Precipitation；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into alphabetical shape with ethyl alcohol
In the mold of shape, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised to 320 under conditions of argon gas or nitrogen with the heating rate of 2 DEG C/min
DEG C DEG C and keep the temperature 2 hours, then with the heating rate of 2 DEG C/min be increased to 800 DEG C and keep the temperature 2 hours to get the three of letter shapes
Tie up graphene.
Experiment eight：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 100mg graphene oxides and 50g dicyandiamides ultrasonic disperse to 0.5L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 0.5mol/L of 0.5L are added in dispersion liquid obtained by step 1, are obtained
To precipitation；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, suction filtration products therefrom is re-dispersed into cylinder with ethyl alcohol
In the mold of shape, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised to 320 under conditions of argon gas or nitrogen with the heating rate of 2 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 800 DEG C with the heating rate of 5 DEG C/min and keep the temperature 2 hours three-dimensionals to get cylindrical shape
Graphene.
Experiment nine：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 100mg graphene oxides and 50g dicyandiamides ultrasonic disperse to 0.2-2L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 1.5mol/L of 0.1L are added in dispersion liquid obtained by step 1, are obtained
To precipitation；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, will suction filtration products therefrom be re-dispersed into ethyl alcohol it is cylindric
Mold in, in 70 DEG C of dry 10h, obtain presoma；
Four, the presoma obtained by step 3 is raised to 350 under conditions of argon gas or nitrogen with the heating rate of 2 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 900 DEG C with the heating rate of 1 DEG C/min and keep the temperature 2 hours to get columned three-dimensional stone
Black alkene.
Experiment ten：
The preparation method of three-dimensional grapheme is to carry out according to the following steps：
One, by 300mg graphene oxides and 30g melamines ultrasonic disperse to 0.2-2L solvents, dispersion liquid is obtained；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 2mol/L of 1L are added in dispersion liquid obtained by step 1, are sunk
It forms sediment；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, will filters products therefrom and be re-dispersed into heart with ethyl alcohol
In mold, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised to 400 under conditions of argon gas or nitrogen with the heating rate of 1 DEG C/min
DEG C and keep the temperature 2 hours, then be increased to 750 DEG C with the heating rate of 2 DEG C/min and keep the temperature 2 hours to get heart-shaped three-dimensional graphite
Alkene.
Claims (10)
1. the method that template prepares three-dimensional grapheme, it is characterised in that the preparation method of three-dimensional grapheme be according to the following steps into
Row：
One, it by 5-500mg graphene oxides and 2.5-50g melamines or dicyandiamide ultrasonic disperse to 0.2-2L solvents, obtains
To dispersion liquid；
Two, the dust technology, dilute sulfuric acid or phosphoric acid of a concentration of 0.1-2mol/L of 0.05-1L are added in dispersion liquid obtained by step 1,
It is precipitated；
Three, precipitation is filtered and with washes of absolute alcohol 3 times, will suction filtration products therefrom be re-dispersed into ethyl alcohol it is of different shapes
In mold, in 70 DEG C of dry 10h, presoma is obtained；
Four, the presoma obtained by step 3 is raised to 300- under conditions of argon gas or nitrogen with the heating rate of 1-2 DEG C/min
400 DEG C and keep the temperature 2 hours, then with the heating rate of 1-5 DEG C/min be increased to 750-900 DEG C and keep the temperature 2 hours to get three-dimensional stone
Black alkene.
2. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that molten described in step 1
Agent is ethylene glycol, water or ethyl alcohol.
3. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that by 200mg oxygen in step 1
In graphite alkene and 30g melamines or dicyandiamide ultrasonic disperse to 1L solvents.
4. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that with 1 DEG C/min in step 4
Heating rate be raised to 310-390 DEG C.
5. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that in step 4 with 1.5 DEG C/
The heating rate of min is raised to 320-380 DEG C.
6. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that with 2 DEG C/min in step 4
Heating rate be raised to 350 DEG C.
7. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that in step 4 again with 1 DEG C/
The heating rate of min is increased to 780 DEG C.
8. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that in step 4 again with 2 DEG C/
The heating rate of min is increased to 800 DEG C.
9. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that in step 4 again with 3 DEG C/
The heating rate of min is increased to 820 DEG C.
10. the method that template prepares three-dimensional grapheme according to claim 1, it is characterised in that in step 4 again with 4 DEG C/
The heating rate of min is increased to 850 DEG C.
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