CN106206052B - A kind of porous carbon composite electrode material of three-dimensional graphite alkenyl N doping and preparation method thereof - Google Patents
A kind of porous carbon composite electrode material of three-dimensional graphite alkenyl N doping and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 21
- 239000010439 graphite Substances 0.000 title claims abstract description 21
- 239000007772 electrode material Substances 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- 239000004964 aerogel Substances 0.000 claims abstract description 28
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
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- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
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- 238000001035 drying Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000012043 crude product Substances 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
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- 230000008569 process Effects 0.000 abstract description 10
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- 238000006243 chemical reaction Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
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- 238000001354 calcination Methods 0.000 description 6
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- 238000002242 deionisation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
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- 238000002604 ultrasonography Methods 0.000 description 4
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- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 230000000802 nitrating effect Effects 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of porous carbon composite electrode materials of three-dimensional graphite alkenyl N doping and preparation method thereof.The present invention is first with graphene oxide (GO) for raw material, and hydro-thermal method obtains graphene hydrogel, and high-temperature process obtains graphene aerogel (GAs) later；Then it is that carbon nitrogen source and graphene aerogel are compound, and high-temperature process obtains NPC GAs with m-phenylene diamine (MPD) (mPD).The present invention not only has big specific surface area, excellent circulation ability using the three-dimensional graphite alkenyl N doping porous carbon NPC GAs composite materials that hydro-thermal is obtained with high-temperature process method, and it is carbon-nitrogen doped make surface charge store fast reaction, shorten transportation route, it is one of ideal energy and material, can be used as electrode material.
Description
Technical field
The invention belongs to materialogy technical fields, are related to a kind of three-dimensional hierarchical structure combination electrode material, specifically
A kind of three-dimensional graphite alkenyl N doping porous carbon composite (NPC-GAs) and preparation method thereof.
Background technology
With the fast development of society, energy and environment are the two big main problems that human kind sustainable development faces.With
Non-renewable energy resources such as oil, natural gas, coal etc. are slowly exhausted, and reproducible clean energy resource is rapidly developed.In new energy
While obtaining broad development, it is also faced with a critical issue for being badly in need of solving：How effectively to store and convert these energy
Amount such as solar energy, wind energy and thermal energy.Therefore energy storage technology becomes the key link of New Energy Industry, and research and development is novel
Energy storage devices are particularly important.Currently, the energy storage technology of ultracapacitor is got growing concern for.Capacitor be between
A kind of new type of energy storage device between traditional capacitor and battery, mainly stores energy by Physical Mechanism, has super large
Capacity, good cycling stability, charge and discharge are fast, high power density and it is environmentally safe the advantages that, now in traffic, military affairs, boat
The fields such as its aviation, electronic device are fully utilized, and become one of the research hotspot of global new energy field.
Most of commercialized electrode material is mainly based on carbon material at present, but its cyclical stability is poor, charge and discharge
The shortcomings of electric overlong time and too small specific surface area, limits its large-scale use.Graphene has big specific surface area, holds
The ionic weight received is big, and superpower electric conductivity and power density are big.And N doping porous carbon can provide the height for accommodating charge
The porous structure of surface area, the carbon atom for adulterating nitrogen provide the electrolyte wettability and electron conduction of enhancing, have simultaneously
High circulation ability so that have good application prospect in electrochemistry.But the nitrating porous carbon that laboratory is studied at present
There are certain defect, the porous carbon skeleton for the NPC that great drawback introduces in the fabrication process that electronics is inevitably hindered to turn
Move and weaken its electro-chemical activity；If the graphene aerogel with three-dimensional macroporous structure combined with nitrating porous carbon, institute
Obtained graded porous structure NPC-GAs combinations, will greatly promote their electrochemical applications.
Invention content
In view of the above technical problems, the purpose of the present invention is to provide a kind of three-dimensional graphite alkenyl N doping porous carbon is compound
Electrode material and preparation method thereof.The composite material that this method obtains has big specific surface area and hierarchical porous structure, increases
The contact area of material and electrolyte is conducive to the quick transmission of electronics；Relatively high nitrogen content, increases reaction active site
Point, to improve the adsorption rate of electronics；Three-dimensional framework graphene is that material has good conductive property and stable circulation simultaneously
Property, it will not cause damages to environment.
The present invention is first with graphene oxide (GO) for raw material, and hydro-thermal method obtains graphene hydrogel, later high-temperature process
Obtain graphene aerogel (GAs)；Then compound for carbon nitrogen source and graphene aerogel with m-phenylene diamine (MPD) (mPD), and at high temperature
Reason obtains NPC-GAs.Specific technical solution of the present invention is described below.
The present invention provides a kind of preparation method of three-dimensional graphite alkenyl N doping porous carbon composite, by by isophthalic
Diamines is compound with graphene aerogel, obtains three-dimensional graphite alkenyl N doping porous carbon composite；It is as follows：
(1) at room temperature, by graphene aerogel GAs in FeCl380-150h is placed in solution, is filtered later, it is dry, it obtains
To the graphene aerogel GAs-Fe of load iron；
(2) it after mixing the graphene aerogel GAs-Fe of load iron with m-phenylene diamine (MPD) mPD, is heat-treated under inert atmosphere,
Obtain crude product；
(3) iron that above-mentioned crude product is removed with diluted acid, is washed with water and washs, dries, and it is porous to obtain three-dimensional graphite alkenyl N doping
Carbon composite.
In above-mentioned steps (1), FeCl3Molar concentration be 1-3mol/L.
In above-mentioned steps (1), graphene aerogel GAs and FeCl3The mass volume ratio of solution is 10：5-1：5mg/mL.
In above-mentioned steps (1), graphene aerogel GAs is using graphene oxide GO as raw material, and first hydro-thermal method obtains graphite
Alkene hydrogel, later heat treatment are prepared.
In above-mentioned steps (1), the preparation method of graphene aerogel GAs is specific as follows：By graphene oxide and F-127 in
After being mixed in water, hydro-thermal reaction 16-20h at a temperature of 175-185 DEG C in water heating kettle obtains graphene hydrogel；4-6 DEG C again/min
Speed be warming up to 650-700 DEG C, keep the temperature 2-3h, obtain graphene aerogel GAs.
In above-mentioned steps (2), the mass ratio of graphene aerogel GAs and m-phenylene diamine (MPD) mPD are 1:1-1:3.
In above-mentioned steps (2), when heat treatment, computer heating control program is：The speed of 4-6 DEG C/min is warming up to 300-700
DEG C, 2-4 hour is kept the temperature later, last Temperature fall.
In above-mentioned steps (3), diluted acid is the dilute hydrochloric acid of 2-6mol/L or the dilute sulfuric acid of 2-6mol/L.
In above-mentioned steps (3), drying temperature is 55-65 DEG C.
The present invention also provides a kind of porous carbon composite electrode materials of three-dimensional graphite alkenyl N doping that above-mentioned preparation method obtains
Material.
The beneficial effects of the present invention are：
The porous carbon composite electrode material of three-dimensional graphite alkenyl N doping that method through the invention obtains, takes full advantage of
The coupling of graphene aerogel and m-phenylene diamine (MPD), the NPC-GAs composite materials obtained using hydro-thermal and high-temperature process method,
Specific surface area is up to 474m2g-1And there is circulation ability outstanding, after 10000 circle of cycle, specific capacity stills remain in 92%.
Meanwhile it is carbon-nitrogen doped can make material surface charge store fast reaction, shorten transportation route, be ideal energy and material it
One.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite materials of 1 gained of embodiment.
Fig. 2 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite materials of 2 gained of embodiment.
Fig. 3 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite materials of 2 gained of embodiment.
Fig. 4 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite materials of 3 gained of embodiment.
Fig. 5 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite materials of 4 gained of embodiment.
Fig. 6 is the NPC-GAs composite material chemical property figures obtained by embodiment 1-4.
Fig. 7 is the NPC-GAs composite material chemical property figures obtained by embodiment 1-4.
Specific implementation mode
It is expanded on further below by specific embodiment and in conjunction with attached drawing to the present invention, but is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of NPC-GAs three-dimensionals hierarchical structure electrode material, includes the following steps：
(1) it includes pre-oxidation and secondary oxygen that the preparation of graphene oxide (GO), which uses improved Hummers methods, synthesis step,
Change.
(2) graphene aerogel (GAs) is prepared：
A. it takes 0.6g polyoxyethylene polyoxypropylene block copolymers (F-127) in 100mL beakers, 20mL deionizations is added
Water, and ultrasound 3h is completely dissolved until F-127 (400mg)；
B. 100mg graphenes are added in the 100mL beakers of a steps, supplement deionized water to 50mL and stirs evenly；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carries out hydro-thermal reaction, reacts 16h at 175 DEG C；
D. the blocks of solid sample obtained is put into glass, is put into freeze-dryer and is dried in vacuo；
E. the sample after drying is taken out, is put into nitrogen furnace and is burnt, overall process nitrogen protection, with 4 DEG C/min's
Speed is warming up to 650 DEG C, and calcination time is 2 hours, is taken out after natural cooling cooling, weighs Mass Calculation yield.
(3) NPC-GAs is prepared：
A. first, the GAs (100mg) that above-mentioned steps (2) obtain is added to FeCl3In (1M, 50mL) solution, in room temperature
Middle placement 80h,
B. the GAs after drying is then weighed, GAs-Fe (150mg) is mixed with the mPD (300mg) after grinding；
C. the mixture of GAs and mPD powder is put into nitrogen furnace, is warming up to 300 under a nitrogen with the speed of 4 DEG C/min
DEG C, two hours are kept the temperature, Temperature fall；
D. the sample obtained in step c the hydrochloric acid of 2M impregnated repeatedly, clean removal iron therein, then use deionization
Water cleans and removes removing chloride repeatedly, and drying in 55 DEG C of baking ovens is put into after, it is multiple both to have obtained three-dimensional graphite alkenyl N doping porous carbon
Condensation material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, NPC-GAs samples are swept
It retouches, the scanning electron microscope (SEM) photograph of gained is indicated above as shown in Figure 1, the as can be seen from Figure 1 three-dimensional sheet structure of composite material
Porous carbon is supported on well on three-dimensional grapheme aeroge, and successfully preparing NPC-GAs has big specific surface area, has simultaneously
There is larger aperture.
Embodiment 2
A kind of preparation method of NPC-GAs three-dimensionals hierarchical structure electrode material, includes the following steps：
(1) it includes pre-oxidation and secondary oxygen that the preparation of graphene oxide (GO), which uses improved Hummers methods, synthesis step,
Change.
(2) graphene aerogel (GAs) is prepared：
A. it takes 0.6gF-127 in 100mL beakers, 20mL deionized waters is added, and ultrasound 3h is until F-127 (500mg)
It is completely dissolved；
B. 100mg graphenes are added in the 100mL beakers of a steps, supplement deionized water to 50mL and stirs evenly；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carries out hydro-thermal reaction, reacts 17h at 180 DEG C；
D. the blocks of solid sample obtained is put into glass, is put into freeze-dryer and is dried in vacuo；
E. the sample after drying is taken out, is put into nitrogen furnace and is burnt, overall process nitrogen protection, with 5 DEG C/min's
Speed is warming up to 680 DEG C, and calcination time is 2.5 hours, is taken out after natural cooling cooling, weighs Mass Calculation yield.
(3) NPC-GAs is prepared：
A. first, the GAs (100mg) that above-mentioned steps (2) obtain is added to FeCl3In (2M, 50mL) solution, in room temperature
Middle placement 100h,
B. the GAs after drying is then weighed, GAs-Fe (150mg) is mixed with the mPD (300mg) after grinding；
C. the mixture of GAs and mPD powder is put into nitrogen furnace, is warming up to 500 under a nitrogen with the speed of 5 DEG C/min
DEG C, two hours are kept the temperature, Temperature fall；
D. the sample obtained in step c the hydrochloric acid of 3M impregnated repeatedly, clean removal iron therein, then use deionization
Water cleans and removes removing chloride repeatedly, and drying in 60 DEG C of baking ovens is put into after, it is multiple both to have obtained three-dimensional graphite alkenyl N doping porous carbon
Condensation material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, NPC-GAs samples are swept
It retouches, the scanning electron microscope (SEM) photograph of gained is as shown in Figure 2,3, the three-dimensional sheet structure of composite material is can be seen that from Fig. 2,3, thus table
Clear porous carbon is supported on well on three-dimensional grapheme aeroge, and successfully preparing NPC-GAs has big specific surface area, together
When have a large amount of microgap hole.
Embodiment 3
A kind of preparation method of NPC-GAs three-dimensionals hierarchical structure electrode material, includes the following steps：
(1) it includes pre-oxidation and secondary oxygen that the preparation of graphene oxide (GO), which uses improved Hummers methods, synthesis step,
Change.
(2) graphene aerogel (GAs) is prepared：
A. it takes 0.6gF-127 in 100mL beakers, 20mL deionized waters is added, and ultrasound 3h is until F-127 (500mg)
It is completely dissolved；
B. 100mg graphenes are added in the 100mL beakers of a steps, supplement deionized water to 50mL and stirs evenly；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carries out hydro-thermal reaction, reacts 18h at 180 DEG C；
D. the blocks of solid sample obtained is put into glass, is put into freeze-dryer and is dried in vacuo；
E. the sample after drying is taken out, is put into nitrogen furnace and is burnt, overall process nitrogen protection, with 5 DEG C/min's
Speed is warming up to 700 DEG C, and calcination time is 2.5 hours, is taken out after natural cooling cooling, weighs Mass Calculation yield.
(3) NPC-GAs is prepared：
A. first, the GAs (100mg) that above-mentioned steps (2) obtain is added to FeCl3In (2M, 50mL) solution, in room temperature
Middle placement 120h,
B. the GAs after drying is then weighed, GAs-Fe (150mg) is mixed with the mPD (200mg) after grinding；
C. the mixture of GAs and mPD powder is put into nitrogen furnace, is warming up to 600 under a nitrogen with the speed of 5 DEG C/min
DEG C, two hours are kept the temperature, Temperature fall；
D. the sample obtained in step c the hydrochloric acid of 4M impregnated repeatedly, clean removal iron therein, then use deionization
Water cleans and removes removing chloride repeatedly, and drying in 60 DEG C of baking ovens is put into after, it is multiple both to have obtained three-dimensional graphite alkenyl N doping porous carbon
Condensation material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, NPC-GAs samples are swept
It retouches, the scanning electron microscope (SEM) photograph of gained is indicated above as shown in figure 4, the as can be seen from Figure 4 three-dimensional sheet structure of composite material
Porous carbon is supported on well on three-dimensional grapheme aeroge, prepare NPC-GAs have big specific surface area, while have compared with
Big aperture.
Embodiment 4
A kind of preparation method of NPC-GAs three-dimensionals hierarchical structure electrode material, includes the following steps：
(1) it includes pre-oxidation and secondary oxygen that the preparation of graphene oxide (GO), which uses improved Hummers methods, synthesis step,
Change.
(2) graphene aerogel (GAs) is prepared：
A. it takes 0.6gF-127 in 100mL beakers, 20mL deionized waters is added, and ultrasound 3h is until F-127 (600mg)
It is completely dissolved；
B. 100mg graphenes are added in the 100mL beakers of a steps, supplement deionized water to 50mL and stirs evenly；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carries out hydro-thermal reaction, reacts 20h at 185 DEG C；
D. the blocks of solid sample obtained is put into glass, is put into freeze-dryer and is dried in vacuo；
E. the sample after drying is taken out, is put into nitrogen furnace and is burnt, overall process nitrogen protection, with 6 DEG C/min's
Speed is warming up to 700 DEG C, and calcination time is 3 hours, is taken out after natural cooling cooling, weighs Mass Calculation yield.
(3) NPC-GAs is prepared：
A. first, the GAs (100mg) that above-mentioned steps (2) obtain is added to FeCl3In (3M, 50mL) solution, in room temperature
Middle placement 150h,
B. the GAs after drying is then weighed, GAs-Fe (150mg) is mixed with the mPD (100mg) after grinding；
C. the mixture of GAs and mPD powder is put into nitrogen furnace, is warming up to 700 under a nitrogen with the speed of 6 DEG C/min
DEG C, two hours are kept the temperature, Temperature fall；
D. the sample obtained in step c the hydrochloric acid of 6M impregnated repeatedly, clean removal iron therein, then use deionization
Water cleans and removes removing chloride repeatedly, and drying in 65 DEG C of baking ovens is put into after, it is multiple both to have obtained three-dimensional graphite alkenyl N doping porous carbon
Condensation material.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, NPC-GAs samples are swept
It retouches, the scanning electron microscope (SEM) photograph of gained is indicated above as shown in figure 5, the as can be seen from Figure 5 three-dimensional sheet structure of composite material
Porous carbon is supported on well on three-dimensional grapheme aeroge, prepare NPC-GAs have big specific surface area, while have compared with
Big aperture.
In conclusion a kind of NPC-GAs three-dimensionals hierarchical structure electrode material for preparing of the present invention have big specific surface area,
Circulation ability outstanding, and it is carbon-nitrogen doped make surface charge store fast reaction.It is tested using three electrode capacitors, electricity
It is 1mol/L H to solve liquid2SO4, normal electrode is inertia Pt electrodes, and reference electrode is Ag/AgCl electrodes, and working electrode is that load is lived
The Pt nets of property substance.Prepared chemical property is as shown in fig. 6, under the sweep speed of 10mV/s, the electrification of each material
The area for learning window is different, and the wherein electrochemical window of NPC-GA-2 is more bigger than other different materials, so 450 DEG C are forged
The chemical property for burning gained NPC-GAs three-dimensional hierarchical structure electrode materials is best；As shown in fig. 7,450 DEG C of calcining gained NPC-
The impedance of GAs three-dimensional hierarchical structure electrode materials is also minimum；As the electron microscope of comparison diagram 1-5 it is found that obtained by 450 DEG C of calcinings
NPC-GAs three-dimensional hierarchical structure electrode materials have a large amount of microgap hole, while N doping porous carbon can be with graphene gas
Gel echos together well.
The above is only that the specific of embodiments of the present invention is enumerated, and appoints made by technical solution according to the present invention
What equivalent transformation, is within the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of the porous carbon composite electrode material of three-dimensional graphite alkenyl N doping, which is characterized in that its pass through by
M-phenylene diamine (MPD) is compound with graphene aerogel, obtains three-dimensional graphite alkenyl N doping porous carbon composite；It is as follows：
(1) at room temperature, by graphene aerogel GAs in FeCl380-150h is placed in solution, is filtered later, it is dry, it is loaded
The graphene aerogel GAs-Fe of iron；
(2) it after mixing the graphene aerogel GAs-Fe of load iron with m-phenylene diamine (MPD) mPD, is heat-treated, obtains under inert atmosphere
Crude product；
(3) iron in above-mentioned crude product is removed with diluted acid, is washed with water and washs, dries, obtain three-dimensional graphite alkenyl N doping porous carbon
Combination electrode material.
2. preparation method according to claim 1, which is characterized in that in step (1), FeCl3Molar concentration be 1-
3mol/L。
3. preparation method according to claim 1, which is characterized in that in step (1), graphene aerogel GAs and FeCl3
The mass volume ratio of solution is 10:5-1:5mg/mL.
4. preparation method according to claim 1, which is characterized in that in step (1), graphene aerogel GAs is with oxygen
Graphite alkene GO is raw material, and first hydro-thermal method obtains graphene hydrogel, and heat treatment later is prepared.
5. preparation method according to claim 1 or 4, which is characterized in that in step (1), the system of graphene aerogel GAs
Preparation Method is specific as follows：After graphene oxide and polyoxyethylene polyoxypropylene block copolymer F-127 are mixed in water, hydro-thermal
Hydro-thermal reaction 16-20h at a temperature of 175-185 DEG C in kettle, obtains graphene hydrogel；The speed of 4-6 DEG C again/min is warming up to
650-700 DEG C, 2-3h is kept the temperature, graphene aerogel GAs is obtained.
6. preparation method according to claim 1, which is characterized in that in step (2), graphene aerogel GAs and isophthalic
The mass ratio of diamines mPD is 1:1-1:3.
7. preparation method according to claim 1, which is characterized in that in step (2), when heat treatment, computer heating control journey
Sequence is：The speed of 4-6 DEG C/min is warming up to 300-700 DEG C, keeps the temperature 2-4 hour later, last Temperature fall.
8. preparation method according to claim 1, which is characterized in that in step (3), diluted acid is the dilute hydrochloric acid of 2-6mol/L
Or the dilute sulfuric acid of 2-6mol/L.
9. preparation method according to claim 1, which is characterized in that in step (3), drying temperature is 55-65 DEG C.
10. the three-dimensional graphite alkenyl N doping porous carbon that a kind of preparation method according to one of claim 1-9 obtains is multiple
Composite electrode material.
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