CN106206052A - A kind of three-dimensional graphite thiazolinyl N doping porous carbon combination electrode material and preparation method thereof - Google Patents
A kind of three-dimensional graphite thiazolinyl N doping porous carbon combination electrode material 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 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007772 electrode material Substances 0.000 title claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 20
- 239000010439 graphite Substances 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 239000004964 aerogel Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000017 hydrogel Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 238000009413 insulation Methods 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
- 239000000463 material Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 5
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000143437 Aciculosporium take Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a kind of three-dimensional graphite thiazolinyl N doping porous carbon combination electrode material and preparation method thereof.The present invention first with graphene oxide (GO) as raw material, hydro-thermal method obtains Graphene hydrogel, and high-temperature process obtains graphene aerogel (GAs) afterwards；Then it is carbon nitrogen source with m-diaminobenzene. (mPD) and graphene aerogel is combined, and high-temperature process obtains NPC GAs.The three-dimensional graphite thiazolinyl N doping porous carbon NPC GAs composite that the present invention uses hydro-thermal and high-temperature process method to obtain not only has big specific surface area, excellent circulation ability, and carbon-nitrogen doped make surface charge store fast reaction, shorten transportation route, it is one of preferable energy and material, can be used as electrode material.
Description
Technical field
The invention belongs to materialogy technical field, relate to a kind of three-dimensional hierarchical structure combination electrode material, specifically
A kind of three-dimensional graphite thiazolinyl N doping porous carbon composite (NPC-GAs) and preparation method thereof.
Background technology
Along with the fast development of society, energy and environment are the two big subject matters that human kind sustainable development faces.Along with
Non-renewable energy resources such as oil, natural gas, coal etc. are slowly exhausted, and reproducible clean energy resource is rapidly developed.At new forms of energy
While obtaining broad development, also it is faced with the key issue being badly in need of solving: the most effectively store and change these energy
Amount is such as solar energy, wind energy and heat energy.Therefore energy storage technology becomes the key link of New Energy Industry, researches and develops novel
Energy storage devices is particularly important.At present, the energy storage technology of ultracapacitor gets growing concern for.Capacitor be between
A kind of novel energy-storing device between traditional capacitor and battery, mainly stores energy by Physical Mechanism, has super large
The advantages such as capacity, good cycling stability, discharge and recharge are fast, high power density and environmentally safe, now in traffic, military affairs, boat
It field such as aviation, electronic device is fully utilized, and becomes one of study hotspot of whole world new energy field.
Current most business-like electrode material mainly material with carbon element is main, but its cyclical stability is poor, charge and discharge
Electricity overlong time and the shortcoming such as specific surface area is too small, limit it and use on a large scale.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 is provided that the height for accommodating electric charge
The loose structure of surface area, the carbon atom of doping nitrogen provides electrolyte wettability and the electron conduction of enhancing, has simultaneously
High circulation ability so that have good application prospect in electrochemistry.But the nitrating porous carbon that laboratory is studied at present is also
Having certain defect, the porous carbon skeleton of the NPC that great drawback introduces in the fabrication process inevitably hinders electronics to turn
Move and weaken its electro-chemical activity；If the graphene aerogel with three-dimensional macroporous structure is combined with nitrating porous carbon, institute
The graded porous structure NPC-GAs combination obtained, will greatly promote their electrochemical applications.
Summary of the invention
For above-mentioned technical problem, it is an object of the invention to provide a kind of three-dimensional graphite thiazolinyl N doping porous carbon and be combined
Electrode material and preparation method thereof.The composite that the method obtains has big specific surface area and hierarchical porous structure, increases
Material and the quick transmission of the contact area of electrolyte, beneficially electronics；Of a relatively high nitrogen content, adds reaction active site
Point, thus improve the adsorption rate of electronics；Three-dimensional framework Graphene is that material has good electric conductivity and stable circulation simultaneously
Property, also environment will not be worked the mischief.
The present invention first with graphene oxide (GO) as raw material, hydro-thermal method obtains Graphene hydrogel, afterwards high-temperature process
Obtain graphene aerogel (GAs)；Then it is carbon nitrogen source with m-diaminobenzene. (mPD) and graphene aerogel is combined, and at high temperature
Reason obtains NPC-GAs.The concrete technical scheme of the present invention is described below.
The present invention provides the preparation method of a kind of three-dimensional graphite thiazolinyl N doping porous carbon composite, and it is by by isophthalic
Diamidogen is combined with graphene aerogel, obtains three-dimensional graphite thiazolinyl N doping porous carbon composite；Specifically comprise the following steps that
(1) under room temperature, by graphene aerogel GAs in FeCl3Solution is placed 80-150h, filters afterwards, be dried,
Graphene aerogel GAs-Fe to load iron；
(2) after the graphene aerogel GAs-Fe of load iron being mixed with m-diaminobenzene. mPD, heat treatment under inert atmosphere,
Obtain crude product；
(3) with diluted acid remove above-mentioned crude product ferrum, be washed with water wash, be dried, obtain three-dimensional graphite thiazolinyl N doping porous
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 with graphene oxide GO as raw material, and first hydro-thermal method obtains graphite
Alkene hydrogel, after-baking prepare.
In above-mentioned steps (1), the preparation method of graphene aerogel GAs is specific as follows: by graphene oxide and F-127 in
In water after mixing, hydro-thermal reaction 16-20h at a temperature of 175-185 DEG C in water heating kettle, obtain Graphene hydrogel；4-6 DEG C again/min
Speed be warming up to 650-700 DEG C, be incubated 2-3h, obtain graphene aerogel GAs.
In above-mentioned steps (2), the mass ratio of graphene aerogel GAs and m-diaminobenzene. mPD is 1:1-1:3.
In above-mentioned steps (2), during heat treatment, its computer heating control program is: the speed of 4-6 DEG C/min is warming up to 300-700
DEG C, insulation afterwards 2-4 hour, last Temperature fall.
In above-mentioned steps (3), diluted acid is dilute hydrochloric acid or the dilute sulfuric acid of 2-6mol/L of 2-6mol/L.
In above-mentioned steps (3), baking temperature is 55-65 DEG C.
The present invention also provides for the three-dimensional graphite thiazolinyl N doping porous carbon combination electrode material that a kind of above-mentioned preparation method obtains
Material.
The beneficial effects of the present invention is:
The three-dimensional graphite thiazolinyl N doping porous carbon combination electrode material obtained by the method for the present invention, is taken full advantage of
Graphene aerogel and the coupling of m-diaminobenzene., use the NPC-GAs composite that hydro-thermal obtains with high-temperature process method, its
Specific surface area is up to 474m2g-1, and there is prominent circulation ability, after circulation 10000 circle, specific capacity stills remain in 92%.
Meanwhile, carbon-nitrogen doped can make material surface electric charge store fast reaction, shorten transportation route, be preferable energy and material it
One.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite of embodiment 1 gained.
Fig. 2 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite of embodiment 2 gained.
Fig. 3 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite of embodiment 2 gained.
Fig. 4 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite of embodiment 3 gained.
Fig. 5 is the scanning electron microscope (SEM) photograph of the NPC-GAs composite of embodiment 4 gained.
Fig. 6 is the NPC-GAs composite chemical property figure of embodiment 1-4 gained.
Fig. 7 is the NPC-GAs composite chemical property figure of embodiment 1-4 gained.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention is expanded on further, but it is not limiting as the present invention.
Embodiment 1
The preparation method of a kind of NPC-GAs three-dimensional hierarchical structure electrode material, comprises the steps:
(1) preparation of graphene oxide (GO) uses the Hummers method improved, and synthesis step includes pre-oxidation and secondary oxygen
Change.
(2) graphene aerogel (GAs) is prepared:
A. take 0.6g polyoxyethylene polyoxypropylene block copolymer (F-127) in 100mL beaker, add 20mL deionization
Water, and ultrasonic 3h is until F-127 (400mg) is completely dissolved；
B. 100mg Graphene is joined in the 100mL beaker of a step, supplement deionized water and to 50mL and stir；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carry out hydro-thermal reaction, at 175 DEG C, react 16h；
D. the blocks of solid sample obtained is put in glass, puts in freeze dryer and is vacuum dried；
E. taking out dried sample, put in nitrogen furnace and burn, overall process nitrogen is protected, with 4 DEG C/min's
Speed is warming up to 650 DEG C, and calcination time is 2 hours, takes out, weigh Mass Calculation productivity after natural cooling cooling.
(3) NPC-GAs is prepared:
First, the GAs (100mg) that above-mentioned steps (2) obtains is joined FeCl3In (1M, 50mL) solution, in room temperature
Middle placement 80h,
The most then weigh dried GAs, GAs-Fe (150mg) is mixed with the mPD (300mg) after grinding；
C. the mixture of GAs Yu mPD powder is put in nitrogen furnace, be warming up to 300 with the speed of 4 DEG C/min under a nitrogen
DEG C, it is incubated two hours, Temperature fall；
D. the hydrochloric acid of the sample 2M obtained in step c soaked repeatedly, clean removal ferrum therein, use deionization subsequently
Water cleans removing chloride repeatedly, after put in 55 DEG C of baking ovens and be dried, both obtained three-dimensional graphite thiazolinyl N doping porous carbon multiple
Condensation material.
Use field emission scanning electron microscope (Germany Zeiss ultra 55) instrument, NPC-GAs sample is swept
Retouching, the scanning electron microscope (SEM) photograph of gained, as it is shown in figure 1, the three-dimensional sheet structure of as can be seen from Figure 1 composite, is indicated above
Porous carbon is supported on three-dimensional grapheme aeroge well, successfully prepares NPC-GAs and has big specific surface area, has simultaneously
There is bigger aperture.
Embodiment 2
The preparation method of a kind of NPC-GAs three-dimensional hierarchical structure electrode material, comprises the steps:
(1) preparation of graphene oxide (GO) uses the Hummers method improved, and synthesis step includes pre-oxidation and secondary oxygen
Change.
(2) graphene aerogel (GAs) is prepared:
A. take 0.6gF-127 in 100mL beaker, add 20mL deionized water, and ultrasonic 3h is until F-127 (500mg)
It is completely dissolved；
B. 100mg Graphene is joined in the 100mL beaker of a step, supplement deionized water and to 50mL and stir；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carry out hydro-thermal reaction, at 180 DEG C, react 17h；
D. the blocks of solid sample obtained is put in glass, puts in freeze dryer and is vacuum dried；
E. taking out dried sample, put in nitrogen furnace and burn, overall process nitrogen is protected, with 5 DEG C/min's
Speed is warming up to 680 DEG C, and calcination time is 2.5 hours, takes out, weigh Mass Calculation productivity after natural cooling cooling.
(3) NPC-GAs is prepared:
First, the GAs (100mg) that above-mentioned steps (2) obtains is joined FeCl3In (2M, 50mL) solution, in room temperature
Middle placement 100h,
The most then weigh dried GAs, GAs-Fe (150mg) is mixed with the mPD (300mg) after grinding；
C. the mixture of GAs Yu mPD powder is put in nitrogen furnace, be warming up to 500 with the speed of 5 DEG C/min under a nitrogen
DEG C, it is incubated two hours, Temperature fall；
D. the hydrochloric acid of the sample 3M obtained in step c soaked repeatedly, clean removal ferrum therein, use deionization subsequently
Water cleans removing chloride repeatedly, after put in 60 DEG C of baking ovens and be dried, both obtained three-dimensional graphite thiazolinyl N doping porous carbon multiple
Condensation material.
Use field emission scanning electron microscope (Germany Zeiss ultra 55) instrument, NPC-GAs sample is swept
Retouch, the scanning electron microscope (SEM) photograph of gained as shown in Figure 2,3, from Fig. 2, the three-dimensional sheet structure that can be seen that composite 3, thus table
Clear porous carbon is supported on three-dimensional grapheme aeroge well, successfully prepares NPC-GAs and has big specific surface area, with
Time there is hole, substantial amounts of microgap.
Embodiment 3
The preparation method of a kind of NPC-GAs three-dimensional hierarchical structure electrode material, comprises the steps:
(1) preparation of graphene oxide (GO) uses the Hummers method improved, and synthesis step includes pre-oxidation and secondary oxygen
Change.
(2) graphene aerogel (GAs) is prepared:
A. take 0.6gF-127 in 100mL beaker, add 20mL deionized water, and ultrasonic 3h is until F-127 (500mg)
It is completely dissolved；
B. 100mg Graphene is joined in the 100mL beaker of a step, supplement deionized water and to 50mL and stir；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carry out hydro-thermal reaction, at 180 DEG C, react 18h；
D. the blocks of solid sample obtained is put in glass, puts in freeze dryer and is vacuum dried；
E. taking out dried sample, put in nitrogen furnace and burn, overall process nitrogen is protected, with 5 DEG C/min's
Speed is warming up to 700 DEG C, and calcination time is 2.5 hours, takes out, weigh Mass Calculation productivity after natural cooling cooling.
(3) NPC-GAs is prepared:
First, the GAs (100mg) that above-mentioned steps (2) obtains is joined FeCl3In (2M, 50mL) solution, in room temperature
Middle placement 120h,
The most then weigh dried GAs, GAs-Fe (150mg) is mixed with the mPD (200mg) after grinding；
C. the mixture of GAs Yu mPD powder is put in nitrogen furnace, be warming up to 600 with the speed of 5 DEG C/min under a nitrogen
DEG C, it is incubated two hours, Temperature fall；
D. the hydrochloric acid of the sample 4M obtained in step c soaked repeatedly, clean removal ferrum therein, use deionization subsequently
Water cleans removing chloride repeatedly, after put in 60 DEG C of baking ovens be dried, both obtained three-dimensional graphite thiazolinyl N doping
Porous carbon
Composite.
Use field emission scanning electron microscope (Germany Zeiss ultra 55) instrument, NPC-GAs sample is swept
Retouching, as shown in Figure 4, as can be seen from Figure 4 the three-dimensional sheet structure of composite, is indicated above the scanning electron microscope (SEM) photograph of gained
Porous carbon is supported on three-dimensional grapheme aeroge well, prepares NPC-GAs and has big specific surface area, has relatively simultaneously
Big aperture.
Embodiment 4
The preparation method of a kind of NPC-GAs three-dimensional hierarchical structure electrode material, comprises the steps:
(1) preparation of graphene oxide (GO) uses the Hummers method improved, and synthesis step includes pre-oxidation and secondary oxygen
Change.
(2) graphene aerogel (GAs) is prepared:
A. take 0.6gF-127 in 100mL beaker, add 20mL deionized water, and ultrasonic 3h is until F-127 (600mg)
It is completely dissolved；
B. 100mg Graphene is joined in the 100mL beaker of a step, supplement deionized water and to 50mL and stir；
C. above-mentioned solution is moved in the water heating kettle of 100mL, carry out hydro-thermal reaction, at 185 DEG C, react 20h；
D. the blocks of solid sample obtained is put in glass, puts in freeze dryer and is vacuum dried；
E. taking out dried sample, put in nitrogen furnace and burn, overall process nitrogen is protected, with 6 DEG C/min's
Speed is warming up to 700 DEG C, and calcination time is 3 hours, takes out, weigh Mass Calculation productivity after natural cooling cooling.
(3) NPC-GAs is prepared:
First, the GAs (100mg) that above-mentioned steps (2) obtains is joined FeCl3In (3M, 50mL) solution, in room temperature
Middle placement 150h,
The most then weigh dried GAs, GAs-Fe (150mg) is mixed with the mPD (100mg) after grinding；
C. the mixture of GAs Yu mPD powder is put in nitrogen furnace, be warming up to 700 with the speed of 6 DEG C/min under a nitrogen
DEG C, it is incubated two hours, Temperature fall；
D. the hydrochloric acid of the sample 6M obtained in step c soaked repeatedly, clean removal ferrum therein, use deionization subsequently
Water cleans removing chloride repeatedly, after put in 65 DEG C of baking ovens and be dried, both obtained three-dimensional graphite thiazolinyl N doping porous carbon multiple
Condensation material.
Use field emission scanning electron microscope (Germany Zeiss ultra 55) instrument, NPC-GAs sample is swept
Retouching, the scanning electron microscope (SEM) photograph of gained, as it is shown in figure 5, the three-dimensional sheet structure of as can be seen from Figure 5 composite, is indicated above
Porous carbon is supported on three-dimensional grapheme aeroge well, prepares NPC-GAs and has big specific surface area, has relatively simultaneously
Big aperture.
In sum, a kind of NPC-GAs three-dimensional hierarchical structure electrode material that prepared by the present invention have big specific surface area,
Prominent circulation ability, and carbon-nitrogen doped make surface charge store fast reaction.Three electrode capacitors are used to test, electricity
Solving liquid is 1mol/L H2SO4, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode, and working electrode is that load is lived
The Pt net of property material.Prepared chemical property as it is shown in fig. 7, under the sweep speed of 10mV/s, the electrification of every kind of material
The area learning window is different, wherein bigger, so 450 DEG C are forged than other different materials of the electrochemical window of NPC-GA-2
The chemical property burning gained NPC-GAs three-dimensional hierarchical structure electrode material is best；450 DEG C of calcining gained NPC-GAs three-dimensional rank
The impedance of Rotating fields electrode material is also minimum；By the Electronic Speculum figure of comparison diagram 1-6,450 DEG C of calcining gained NPC-GAs tri-
That ties up hierarchical structure electrode material has hole, substantial amounts of microgap, and N doping porous carbon can with graphene aerogel well simultaneously
Echo together.
Specifically enumerating of foregoing only embodiments of the present invention, and according to appointing that technical scheme is made
What equivalent transformation, all should belong to protection scope of the present invention.
Claims (10)
1. the preparation method of a three-dimensional graphite thiazolinyl N doping porous carbon combination electrode material, it is characterised in that it passes through will
M-diaminobenzene. is combined with graphene aerogel, obtains three-dimensional graphite thiazolinyl N doping porous carbon composite；Specifically comprise the following steps that
(1) under room temperature, by graphene aerogel GAs in FeCl3Solution is placed 80-150h, filters afterwards, be dried, loaded
The graphene aerogel GAs-Fe of ferrum；
(2) after the graphene aerogel GAs-Fe of load iron being mixed with m-diaminobenzene. mPD, heat treatment under inert atmosphere, obtain
Crude product；
(3) remove the ferrum in above-mentioned crude product with diluted acid, be washed with water and wash, be dried, obtain three-dimensional graphite thiazolinyl N doping porous carbon
Combination electrode material.
Preparation method the most according to claim 1, it is characterised in that in step (1), FeCl3Molar concentration be 1-
3mol/L。
Preparation method the most according to claim 1, it is characterised in that in step (1), graphene aerogel GAs and FeCl3
The mass volume ratio of solution is 10:5-1:5mg/mL.
Preparation method the most according to claim 1, it is characterised in that in step (1), graphene aerogel GAs is with oxygen
Functionalized graphene GO is raw material, and first hydro-thermal method obtains Graphene hydrogel, after-baking prepare.
5. according to the preparation method described in claim 1 or 4, it is characterised 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 being mixed in water, hydro-thermal
Hydro-thermal reaction 16-20h at a temperature of 175-185 DEG C in still, obtains Graphene hydrogel；The speed of 4-6 DEG C again/min is warming up to
650-700 DEG C, it is incubated 2-3h, obtains graphene aerogel GAs.
Preparation method the most according to claim 1, it is characterised in that in step (2), graphene aerogel GAs and isophthalic
The mass ratio of diamidogen mPD is 1:1-1:3.
Preparation method the most according to claim 1, it is characterised in that in step (2), during heat treatment, its computer heating control journey
Sequence is: the speed of 4-6 DEG C/min is warming up to 300-700 DEG C, insulation afterwards 2-4 hour, last Temperature fall.
Preparation method the most according to claim 1, it is characterised 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.
Preparation method the most according to claim 1, it is characterised in that in step (3), baking temperature is 55-65 DEG C.
10. the three-dimensional graphite thiazolinyl N doping porous carbon obtained according to the preparation method one of claim 1-9 Suo Shu is again
Composite electrode material.
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| CN106960729A (en) * | 2017-01-25 | 2017-07-18 | 广西大学 | A kind of preparation method of nitrogen sulphur codope carbon material |
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| CN108975301A (en) * | 2018-06-27 | 2018-12-11 | 东华大学 | A kind of graphene with high rate capability/polyimide-based nitrogen-doped carbon aeroge and its preparation and application |
| CN109607690A (en) * | 2018-11-20 | 2019-04-12 | 陕西科技大学 | A kind of preparation method of three-dimensional porous graphene hydrogel antimony-doped tin oxide electrode |
| CN109786771A (en) * | 2019-01-28 | 2019-05-21 | 西安科技大学 | A kind of preparation method of N doping three-dimensional grapheme base fuel battery cathod catalyst |
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