CN106356197A - Preparation method of nitrogen-doped porous carbon sheet layer material loaded with conductive macromolecules - Google Patents

Preparation method of nitrogen-doped porous carbon sheet layer material loaded with conductive macromolecules Download PDF

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Publication number
CN106356197A
CN106356197A CN201611096497.7A CN201611096497A CN106356197A CN 106356197 A CN106356197 A CN 106356197A CN 201611096497 A CN201611096497 A CN 201611096497A CN 106356197 A CN106356197 A CN 106356197A
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sio
preparation
sheet layer
porous carbon
gelatin
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CN201611096497.7A
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范磊
杨莉
徐祥东
徐志龙
郭荣
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Yangzhou University
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Yangzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method of a nitrogen-doped porous carbon sheet layer material loading conductive macromolecules, and relates to the technical field of preparation of super capacitor electrode materials. The method comprises the following steps: by taking gelatin as a carbon/nitrogen source and taking SiO2 as a template, carrying out self assembly of the gelatin, and carbonizing at high temperature to form a sheet layer structure; then etching and removing SiO2 via an NaOH solution to obtain the nitrogen-doped porous carbon sheet layer material with uniform pore size; modifying 2,5-methoxy-1,4-benzoquinone (DMQ) on the surface of the prepared material via a hydrothermal method. The electrode material prepared by the method is large in specific surface area and high in nitrogen doping amount; meanwhile, the electrode material also loads a high-activity aromatic oxidation reduction organic material; through synergism of a plurality of factors, a carbon material with high specific capacitance, high energy density, high power density and high cycle performance can be obtained.

Description

A kind of preparation method of load conducting polymer N doping porous carbon sheet layer material
Technical field
The present invention relates to the preparing technical field of electrode material for super capacitor.
Background technology
Carbon-based supercapacitor can provide higher power density and long cycle life, but due to the storage of electric double layer electric charge Mechanism, they show relatively low energy density compared with battery.Substitute activated carbon using Graphene and be used as business super capacitor Device electrode can increase electric capacity, but it is insufficient for energy increasing need.In order to extend answering of ultracapacitor With, particularly have in the confined space can application in portable and flexible device, exploitation had more compared with double layer capacitor The electrode material of high-energy-density is necessary.In order to solve these problems, fake capacitance material such as metal-oxide or Electro-chemical activity organic material obtains extensive concern, because they pass through surface oxidation reduction process provides extra electric charge storage Capacity.Aromatic series redox active organic material such as quinone etc., due to its safety, low cost and environmental friendliness, is widely used in replacing For reactive metal oxides.When quinone and material with carbon element compound tense it is provided that good high rate performance and cyclicity.Wherein the former Allow the 2e of Rapid reversible-/2h+Redox reaction, the latter provides conductive carrier to stop degraded during quinone circulation.Wherein, 2, 5- dimethoxy-Isosorbide-5-Nitrae-benzoquinone unique structure, it can serve as sept to avoid carbon plate strata collection in the composite, thus There is provided and shorten the passage of ion transmission, provide redox active functional group to promote reversible Faradaic processes and then carry simultaneously The ratio electric capacity of high material and energy density.
Content of the invention
For solving the above problems, present invention aim at proposing a kind of load conducting polymer N doping porous carbon lamella material The preparation method of material.
The present invention comprises the following steps:
1) under stirring condition, by gelatin and sio2It is scattered in deionized water, obtains colloidal sol, colloidal sol is laid on glass plate, After drying, membrane product is scraped from glass plate；
2) under nitrogen protection, membrane product is placed in calcining, prepared sio in vacuum tube furnace2/ c sheet material；
3) by sio2/ c sheet layer material is placed in after soaking in naoh aqueous solution, washs to neutrality, then dries, obtains final product N doping porous Carbon plate layer material；
4), under ultrasound condition, N doping porous carbon sheet layer material and 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone (dmq) are mixed in deionization In water, under the conditions of 160 ± 5 DEG C, then carry out hydro-thermal reaction；Reaction is cooled to room temperature after terminating, and takes solid phase, with deionized water Centrifuge washing, drying, both must load conducting polymer N doping porous carbon sheet layer material (dmq@n-p-css).
The present invention adopts template and hydro-thermal method, with sio2For pore creating material, with gelatin mixing knifing, form lamellar structure. After high-temperature calcination carbonization, the nitrogen-doped carbon material that obtains.Then, after through naoh etching, obtain N doping porous carbon lamella material Material.Finally, modify above-mentioned prepared material using hydro-thermal method 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone (dmq), obtain final product dmq@n-p- Css material.
Wherein, the temperature conditionss of hydro-thermal reaction are 160 ± 5 DEG C, if temperature is too low, the response time can be made to extend, otherwise dmq Carbon material surface can not be loaded to completely；Temperature too high although the response time can shorten, but dmq sample can decompose, and High temperature can destroy the crystal formation of material with carbon element, and time consumption and energy consumption.
Method for designing of the present invention is safe and simple, environmental protection.The lamella material with carbon element thickness that the present invention makes is at 1.5 μm about, interior Portion is sio2The pore passage structure being formed after removing, material surface loads dmq.Dmq@n-p-css material using present invention preparation As the electrode material of ultracapacitor, there is high specific capacitance and energy density.
Further, in step 1) of the present invention, gelatin and sio2Feed intake mass ratio be 2: 1, for scattered sio2Grain Footpath is 20 ± 2nm.I.e. gelatin and sio in mixed system2Mass ratio is 2: 1.Under this ratio, using the collosol and gel of gelatin Property, gelatin molecule is equably arranged in layer structure.Gelatin is to obtain carbon material surface to have more as carbon source and nitrogen source purpose Many nitrogen-containing functional groups, increase the electric conductivity of material, the N doping porous carbon sheet layer material capacitive character that this mass ratio prepares Can be optimum.Shown by elementary analysiss and nitrogen adsorption desorption test result: using the sio for 20 ± 2nm for the particle diameter2Obtained material Material has a higher nitrogen content (6.3%), appropriate aperture (10.8 nm), larger specific surface area (473 m2/ g) and hole body Long-pending (1.19 cm3/ g).Therefore, the sio being 20 nm with particle diameter2The electrode material electric conductivity preparing as perforate template is good Good, good stability bigger than electric capacity.
In order to improve uniformity of mixture, the present invention when preparing colloidal sol, gelatin is dissolved in deionized water formed bright Sol solution, by sio2It is scattered in formation sio in deionized water2Dispersion liquid, then by sio2Dispersion liquid is mixed with gelatin solution, The temperature of mixed system is stirred under conditions of being 60 DEG C reacting, and obtains colloidal sol.
It is highly preferred that the present invention is in described step 1), in institute's gelatine solution, gelatin mass concentration is 20g/l, described sio2Sio in dispersion liquid2Mass fraction is 40%.Viscosity of mixed liquid can be made suitable, the lamellar spacing that knifing obtains is homogeneous, and sio2 Lamella is uniformly dispersed.
In described step 1), described baking temperature is 40 DEG C.In this baking temperature condition, mixed liquor can be laid in glass It is dried in glass plate and drying time is moderate.As temperature is too high, the triple-helix structure of gelatin can be untied, the shape of impact carbon fiber Become.As temperature is too low, gelatin and sio2Dispersion liquid mixed liquor can occur solidification it is impossible to be sprawled on a glass.
Described step 2) in, during described calcining, insulation 2h after 800 DEG C is warming up to the heating rate of 5 DEG C/min.The present invention When calcining under the conditions of temperature is 800 DEG C, degree of carbonization highest.Calcining heat is too high, carbon/nitrogen can be made to run off serious；Forge Burning temperature is too low, and in material with carbon element, impurity is more, and degree of carbonization is low, and degree of graphitization is relatively low.Meanwhile, with 5 DEG C/min for intensification During speed, both can guarantee that gelatin polycondensation and carbonization in pyrolytic process generated material with carbon element, material in pyrolysis can also have been reduced simultaneously Carbon loss vector.If heating rate is excessively slowly although the carbon loss vector of material reduces, but calcination time is long, takes.If heating up speed Rate is too fast although calcination time can reduce, but the loss of the carbon content of material is serious, and macropore increases, and specific surface area reduces, simultaneously Yield is too low.
In described step 3), the concentration of described naoh aqueous solution is 1m, and soaking temperature is 80 DEG C, and the time is 2 ± 0.1h. The addition of naoh is to remove sio for etching2, the naoh solution of low concentration.Improve temperature and can shorten etch period, 80 DEG C of temperature Degree is more suitable.Response time is for guaranteeing sio for 2 ± 0.1h2Etched removing completely.
In described step 3), the temperature conditionss of described drying are 60 ± 5 DEG C.If temperature is too low, sample drying time can be made Long；Temperature is too high can be shortened although drying sample time, but sample is easily reunited, and can destroy the crystal formation of sample. Drying time is too short to make moisture in sample not eliminate, and overlong time also can make sample reunite and time consumption and energy consumption.
In described step 4), material with carbon element and 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone (dmq) feed intake mass ratio for 1: 0.5～1.5. If dmq consumption is too small, dmq load capacity is not enough, causes finally the ratio electric capacity of prepared sample and energy density increase inconspicuous；If Dmq consumption is excessive, and dmq addition exceedes the load capacity of material with carbon element, can make raw material reaction not exclusively, and dmq runs off seriously, wastes Raw material.
In described step 4), described centrifugal rotational speed is 3000r/min, and the time is 5min, and the temperature conditionss of described drying are 60±5℃.
In addition, in described step 4), described ultrasonic power is 80w, the time is 30min；Described centrifugal rotational speed is 3000r/min；The temperature conditionss of described drying are 60 ± 5 DEG C.
In described step 4), if the described ultrasonic time is too short, sample can be made to disperse in deionized water uneven；Ultrasonic If time long although sample dispersion uniformly, but lamella material with carbon element is easily broken, fracture.
If centrifugal rotational speed is too small, centrifugation time is long, sample can be made to be not easy to deposit to centrifugation bottom of the tube, impurity is not easy It is removed；If centrifugal rotational speed is excessive, and although the time can be substantially reduced, but sample is easily reunited it is not easy to spread out, and Some impurity also can be got off by centrifugation, is also not easy to separate sample with impurity.
Brief description
The sem of load conducting polymer N doping porous carbon sheet layer material (dmq@n-p-css) that Fig. 1 is prepared for the present invention Figure.
The tem figure of the dmq@n-p-css material that Fig. 2 is prepared for the present invention.
The X-ray diffraction figure of the dmq@n-p-css material that Fig. 3 is prepared for the present invention.
The ftir figure of the dmq@n-p-css material that Fig. 4 is prepared for the present invention.
The bet figure of the dmq@n-p-css material that Fig. 5 is prepared for the present invention.
Specific embodiment
First, preparation technology:
1st, embodiment 1:
(1) prepare sio2/ gelatin mixed solution:
0.5g gelatin is dissolved in 25ml deionized water solution, is stirred until homogeneous at 60 DEG C, obtaining mass concentration is the bright of 20g/l Sol solution.
0.4g particle diameter is the sio of 20 ± 2nm2It is added in 1ml deionized water, ultrasonic 1 h makes sio2Dispersed, obtain Mass fraction is 40% sio2Dispersion liquid.
Sio by 0.625g2Dispersion liquid be added in 25ml gelatin solution, at 60 DEG C react 30min, reaction terminate after It is cooled to room temperature, obtain colloidal sol as presoma.Then the presoma of cooling is laid on glass plate, and puts into 40 DEG C of baking ovens It is dried.Finally film is scraped, collect standby.
(2) prepare sio2/ c lamella:
Take above-mentioned prepared film to be placed in vacuum tube furnace, be passed through nitrogen 20min, then the heating rate liter with 5 DEG C/min in advance Temperature keeps 2 h, gained black fiber film, i.e. sio to 800 DEG C2/ c lamella.
(3) prepare N doping porous fibre:
Take sio prepared above2/ c lamella 100 mg, is placed in the 10ml naoh aqueous solution that concentration is 1m, in 80 DEG C of water-baths Soak 2 ± 0.1h.It is cooled to room temperature, deionized water is washed till neutrality, be placed in 60 ± 5 DEG C of baking ovens and 12 hs are dried, obtain final product nitrogen and mix Miscellaneous porous carbon sheet layer material.
4) prepare dmq@n-p-css material
Above-mentioned prepared N doping porous carbon sheet layer material and 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone (dmq) are pressed the mass ratio of 1:0.5 It is mixed in deionized water, be transferred in reactor after ultrasonic middle process 30 min for 80w for the power, 160 ± 5 DEG C of hydro-thermals are anti- Answer 16h.Question response is cooled to room temperature after terminating, and using deionized water, with 3000r/min centrifuge washing three times, takes solid phase Dry under the conditions of 60 ± 5 DEG C, obtain final product dmq@n-p-css material.
2nd, embodiment 2:
(1) prepare sio2/ gelatin mixed solution:
0.5g gelatin is dissolved in 25 ml deionized water solutions, is stirred until homogeneous at 60 DEG C, obtaining mass concentration is 20 g/l Gelatin solution.
0.4g particle diameter is the sio of 20 ± 2 nm2It is added in 1ml deionized water, ultrasonic 1h makes sio2Dispersed, obtain Mass fraction is 40% sio2Dispersion liquid.
Sio by 0.625g2Dispersion liquid be added in 25 ml gelatin solutions, react 30min at 60 DEG C, reaction terminates After be cooled to room temperature, obtain substantial amounts of colloidal sol as presoma.Then the presoma of cooling is laid on glass plate, and puts into 40 DEG C of oven dryings.Finally film is scraped, collect standby.
(2) prepare sio2/ c lamella:
Take film prepared above to be placed in vacuum tube furnace, be passed through nitrogen 20min, then the heating rate liter with 5 DEG C/min in advance Temperature keeps 2 h, gained black fiber film, i.e. sio to 800 DEG C2/ c lamella.
(3) prepare N doping porous fibre:
Take sio prepared above2/ c lamella 100 mg, is placed in the 10ml naoh aqueous solution that concentration is 1m, in 80oC water-bath Middle immersion 2 ± 0.1h.It is cooled to room temperature, deionized water is washed till neutrality, is placed in 60 ± 5o12 hs are dried in c baking oven, obtain final product N doping porous carbon sheet layer material.
4) prepare dmq@n-p-css material
Above-mentioned material and 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone (dmq) are mixed in deionized water by the mass ratio of 1:1, It is transferred in reactor after ultrasonic middle process 30 min for 80w in power, carry out hydro-thermal reaction 16h under the conditions of 160 ± 5 DEG C. Question response is cooled to room temperature after terminating, and using deionized water, with 3000r/min centrifuge washing three times, takes solid phase in 60 ± 5 Dry under the conditions of DEG C, obtain final product dmq@n-p-css material.
3rd, enforcement 3:
(1) prepare sio2/ gelatin mixed solution:
0.5 g gelatin is dissolved in 25 ml deionized water solutions, is stirred until homogeneous at 60 DEG C, obtaining mass concentration is 20g/l's Gelatin solution.
0.4g particle diameter is the sio of 20 ± 2 nm2It is added in 1ml deionized water, ultrasonic 1h makes sio2Dispersed, obtain Mass fraction is 40% sio2Dispersion liquid.
Sio by 0.625g2Dispersion liquid be added in 25 ml gelatin solutions, react 30 min at 60 DEG C, reaction terminates After be cooled to room temperature, obtain substantial amounts of colloidal sol as presoma.Then the presoma of cooling is laid on glass plate, and puts into 40 DEG C of oven dryings.Finally film is scraped, collect standby.
(2) prepare sio2/ c lamella:
Take film prepared above to be placed in vacuum tube furnace, be passed through nitrogen 20 min, then the heating rate liter with 5 DEG C/min in advance Temperature keeps 2 h, gained black fiber film, i.e. sio to 800 DEG C2/ c lamella.
(3) prepare N doping porous fibre:
Take sio prepared above2/ c lamella 100 mg, is placed in the 10 ml naoh aqueous solutions that concentration is 1 m, in 80 DEG C of water-baths Middle immersion 2 ± 0.1 h.It is cooled to room temperature, deionized water is washed till neutrality, be placed in 60 ± 5 DEG C of baking ovens and 12 hs are dried, obtain final product nitrogen Doping porous carbon sheet layer material.
4) prepare dmq@n-p-css material
Above-mentioned material and 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone (dmq) are mixed in deionized water by 1:1.5 mass ratio, Power is transferred in reactor for after ultrasonic 30 min under conditions of 80w, carries out hydro-thermal reaction 16 h under the conditions of 160 DEG C.Treat Reaction is cooled to room temperature after terminating, and using deionized water, with 3000r/min centrifuge washing three times, takes solid phase in 60 ± 5 DEG C Under the conditions of dry, obtain final product dmq@n-p-css material.
2nd, product property:
Fig. 1 is the tem figure using the dmq@n-p-css material that each example method is made above.It can be seen that sio2It is eclipsed The porous flake material with carbon element carbon-coating obtaining after quarter is very thin, there is certain overlap, is clear that internal homogeneous circular port knot Structure.After dmq hydro-thermal reaction, flaky material overlap is inconspicuous, and there is increase tendency in aperture.
Fig. 2 is the sem figure using the dmq@n-p-css material that each example method is made above.It can be seen that porous After load dmq, macro morphology significantly to change lamella material with carbon element does not occur, and material surface has sio2Stay after being etched Under uniform mesoporous.
Fig. 3 is the X-ray diffraction figure using the dmq@n-p-css material that each example method is made above.Spread out according to x- ray Penetrate result to understand, the dmq@n-p-css material that the present invention prepares, substantially conform to standard card contrast, substantially demonstrate institute Obtain composition and the structure of material.
Fig. 4 is the ftir figure using the dmq@n-p-css material that each example method is made above.According to infrared results, The dmq@n-p-css material that the present invention prepares, is contrasted it was demonstrated that dmq successfully bears with pure material dmq and porous carbon materials It is downloaded to porous sheet carbon material surface.
Fig. 5 is the bet figure using the dmq@n-p-css material that each example method is made above.It can be seen that sample Adsorption and desorption isotherms belong to brunauer classification iv type, and relative pressure be 0.4～1.0 scope between exist substantially delayed Ring, illustrates that nitrogen dmq@n-p-css material has uniform mesopore model structure, and the pore size distribution range of material is narrower.

Claims (10)

1. a kind of preparation method of load conducting polymer N doping porous carbon sheet layer material is it is characterised in that include following walking Rapid:
1) under stirring condition, by gelatin and sio2It is scattered in deionized water, obtains colloidal sol, colloidal sol is laid on glass plate, warp After drying, membrane product is scraped from glass plate；
2) under nitrogen protection, membrane product is placed in calcining, prepared sio in vacuum tube furnace2/ c sheet material；
3) by sio2/ c sheet layer material is placed in after soaking in naoh aqueous solution, washs to neutrality, then dries, obtains final product N doping porous Carbon plate layer material；
4), under ultrasound condition, N doping porous carbon sheet layer material and 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone are mixed in deionized water, Then carry out hydro-thermal reaction under the conditions of 160 ± 5 DEG C；Reaction is cooled to room temperature after terminating, and takes solid phase, is washed with deionized water centrifugation Wash, dry, both must load conducting polymer N doping porous carbon sheet layer material.
2. according to claim 1 the preparation method of material it is characterised in that in described step 1), gelatin and sio2Feed intake Mass ratio is 2: 1, for scattered sio2Particle diameter be 20 ± 2nm.
3. the preparation method of material according to claim 1 or claim 2 is it is characterised in that in described step 1), gelatin is dissolved in Form gelatin solution, by sio in ionized water2It is scattered in formation sio in deionized water2Dispersion liquid, then by sio2Dispersion liquid with bright Sol solution mixes, and is stirred reacting, obtains colloidal sol under conditions of the temperature of mixed system is 60 DEG C.
4. the preparation method of material is it is characterised in that in described step 1), bright in institute's gelatine solution according to claim 3 Glue mass concentration is 20g/l, described sio2Sio in dispersion liquid2Mass fraction is 40%.
5. according to claim 1 the preparation method of material it is characterised in that in described step 1), described baking temperature is 40 ℃.
6. according to claim 1 the preparation method of material it is characterised in that described step 2) in, during described calcining, with 5 DEG C/heating rate of min is incubated 2h after being warming up to 800 DEG C.
7. according to claim 1 the preparation method of material it is characterised in that in described step 3), described naoh aqueous solution Concentration is 1m, and soaking temperature is 80 DEG C, and the time is 2 ± 0.1h.
8. according to claim 1 the preparation method of material it is characterised in that in described step 3), the temperature strip of described drying Part is 60 ± 5 DEG C.
9. according to claim 1 the preparation method of material it is characterised in that in described step 4), described N doping porous carbon The mixing quality of sheet layer material and 2,5- methoxyl group-Isosorbide-5-Nitrae-benzoquinone is than for 1: 0.5～1.5.
10. it is characterised in that in described step 4), described ultrasonic power is 80w to preparation method according to claim 1, Time is 30 min；Described centrifugal rotational speed is 3000r/min, and the temperature conditionss of described drying are 60 ± 5 DEG C.
CN201611096497.7A 2016-12-02 2016-12-02 Preparation method of nitrogen-doped porous carbon sheet layer material loaded with conductive macromolecules Pending CN106356197A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110357088A (en) * 2019-08-20 2019-10-22 中国科学院长春应用化学研究所 A kind of method and application preparing graphene oxide based on gelatin

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CN104466134A (en) * 2014-12-16 2015-03-25 华东理工大学 Preparation method of self-supported graphene/carbon nano tube hybrid foam-loaded amino-anthraquinone polymer
CN105374575A (en) * 2015-01-14 2016-03-02 中国石油大学(华东) Method for preparing surface-functionalized porous carbon super capacitor electrode material
CN106082161A (en) * 2016-06-06 2016-11-09 扬州大学 A kind of preparation method of N doping porous carbon sheet layer material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090059474A1 (en) * 2007-08-27 2009-03-05 Aruna Zhamu Graphite-Carbon composite electrode for supercapacitors
CN104466134A (en) * 2014-12-16 2015-03-25 华东理工大学 Preparation method of self-supported graphene/carbon nano tube hybrid foam-loaded amino-anthraquinone polymer
CN105374575A (en) * 2015-01-14 2016-03-02 中国石油大学(华东) Method for preparing surface-functionalized porous carbon super capacitor electrode material
CN106082161A (en) * 2016-06-06 2016-11-09 扬州大学 A kind of preparation method of N doping porous carbon sheet layer material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110357088A (en) * 2019-08-20 2019-10-22 中国科学院长春应用化学研究所 A kind of method and application preparing graphene oxide based on gelatin

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