CN103480406A - Nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper and preparation method thereof - Google Patents
Nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper and preparation method thereof Download PDFInfo
- Publication number
- CN103480406A CN103480406A CN201310390188.0A CN201310390188A CN103480406A CN 103480406 A CN103480406 A CN 103480406A CN 201310390188 A CN201310390188 A CN 201310390188A CN 103480406 A CN103480406 A CN 103480406A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- oxide
- carbon nanometer
- doped
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper, which comprises the following steps: a) preparing a graphene oxide dispersion solution; b) preparing an oxidized carbon nanotube dispersion solution; c) mixing the graphene oxide dispersion solution and oxidized carbon nanotube dispersion solution with a cobalt nitrate water solution to obtain a slurry, applying the slurry onto a substrate, and drying to obtain the cobalt-ion-containing graphene oxide/oxidized carbon nanotube composite paper; and d) immersing the cobalt-ion-containing graphene oxide/oxidized carbon nanotube composite paper in an ammonia water solution, and carrying out hydrothermal reaction to obtain the final nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper. The method is simple to operate and mild in reaction conditions, can implement large-scale preparation of soft composite paper with favorable ORR catalytic property, and has favorable application prospects in the field of electrocatalysis.
Description
Technical field
The invention belongs to technical field of nano material, relate more specifically to a kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper and preparation method thereof.
Background technology
Negative electrode oxygen reduction reaction (ORR) eelctro-catalyst is one of key component in fuel cell and other electrochemical appliances.Develop effective ORR eelctro-catalyst the commercialization of fuel cell is played to vital effect.Platinum-base material is studied for a long period of time because of its high catalytic activity, yet the cost of platinum is high, and very responsive to methyl alcohol and CO, and poor durability has hindered the large-scale application of fuel cell.In order to overcome this obstacle, the researcher develops multiple ORR catalyst, such as perovskite, spinelle, nitrogen-doped carbon material etc.Yet current catalyst material still can not meet the demands such as activity is high, cost is low, durable fully.
Recently, the nitrogen-doped carbon material particularly nitrogen-doped graphene as the ORR eelctro-catalyst, be widely studied.Except itself has catalytic activity, nitrogen-doped graphene, because electric conductivity is high, specific area is large, chemical stability is good, to plurality of advantages such as the catalyst granules adhesion are strong, becomes the ideal material of the advanced eelctro-catalyst of preparation.Such as, transition metal oxide/sulfide nano crystal (such as, Co
3o
4, MnCo
2o
4, Fe
3o
4and Co
1 – xs) hybrid material formed with nitrogen-doped graphene, as non-precious metal catalyst, shows excellent ORR electro catalytic activity, and methanol tolerance performance and stability all are better than business Pt/C catalyst.The electro catalytic activity of these hybrid materials is better than independent catalyst granules and nitrogen-doped graphene.Britain's " nature material " (Nature Materials for example, within 2011,10 volume is 780 pages) to have reported and adopt two step solution phase methods to prepare nitrogen-doped graphene/cobaltosic oxide hybrid material, this material demonstrates good electro catalytic activity and is better than the stability of business Pt/C in alkaline solution.
On the other hand, the composite consisted of Graphene and CNT is widely used in the fields such as photocatalysis, lithium ion battery, ultracapacitor and fuel cell.CNT is present between graphene nanometer sheet not only can prevent that Graphene is stacking, increases the basal plane spacing, and has improved electric conductivity.The chemical property of the composite that therefore, Graphene and CNT form often is better than independent Graphene.Such as, Germany " advanced material " (Advanced Materials, 3192 pages of 23 phases in 2013) reported by gentle water-heat process and made nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe nano composite material, wherein nitrogen-doped graphene and nitrogen-doped carbon nanometer pipe have chemiluminescence aspect the ORR catalytic activity.
In addition, the ORR catalyst of report is mostly dusty material at present, during the preparation work electrode, for dusty material being prepared into to uniform dispersion liquid, need carry out ultrasonic for a long time.And the graphene-based paper of self-supporting can be avoided common tediously long electrode production process as the ORR catalyst.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide the preparation method of a kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper.
Another object of the present invention is to provide a kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper.Due to the cooperative effect between nitrogen-doped graphene, nitrogen-doped carbon nanometer pipe and three components of cobaltosic oxide, this extrusion coating paper shows good ORR catalytic performance, is better than the extrusion coating paper that two components of nitrogen-doped graphene and cobaltosic oxide form.
In order to realize purpose of the present invention, at first, the invention provides the preparation method of a kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper, it comprises the following steps:
A. prepare the graphene oxide dispersion liquid;
B. prepare the oxide/carbon nanometer tube dispersion liquid;
C. described graphene oxide dispersion liquid, oxide/carbon nanometer tube dispersion liquid and cobalt nitrate solution are mixed to get to slurry, then described slurry are coated on substrate, then dried to obtain the graphene oxide that comprises cobalt ions/oxide/carbon nanometer tube extrusion coating paper;
D. the graphene oxide by will comprise cobalt ions/oxide/carbon nanometer tube extrusion coating paper immerses and carries out hydro-thermal reaction in the aqueous solution of ammonia and obtain described nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper.
Preferably, in described step a, described graphene oxide dispersion liquid provides by following steps:
A1. strong acid is poured in graphite scale and the mixture of nitrate as sodium nitrate or potassium nitrate as the concentrated sulfuric acid, stirred and obtain dispersion liquid;
A2. in the described dispersion liquid of a1, add strong oxidizer as potassium permanganate, stir, place a period of time, obtain the aubergine pastel;
A3. add successively deionized water and hydrogen peroxide in the described aubergine pastel of a2, obtain glassy yellow suspension;
A4. the described glassy yellow suspension of a3 is centrifugal, the washing and the dialysis, obtain described graphene oxide dispersion liquid.
Preferably, in described step b, described oxide/carbon nanometer tube dispersion liquid provides by following steps:
B1. strong acid is poured in CNT and the mixture of nitrate as sodium nitrate or potassium nitrate as the concentrated sulfuric acid, stirred and obtain dispersion liquid;
B2. in the described dispersion liquid of b1, add strong oxidizer as potassium permanganate, stir, obtain the black pastel;
B3. add successively deionized water and hydrogen peroxide in the described black pastel of b2, obtain black suspension;
B4. the described black suspension suction filtration of b3, washing are obtained to described oxide/carbon nanometer tube dispersion liquid.
Preferably, in described step a, the concentration of described graphene oxide dispersion liquid is 1-6mg/mL.
Preferably, in described step b, the concentration of described oxide/carbon nanometer tube dispersion liquid is 1-10mg/mL.
Preferably, in described step c, described graphene oxide, oxide/carbon nanometer tube mass ratio are 15:1-5:1.
Preferably, in described step c, the mass ratio of described graphene oxide and cobalt nitrate is 17:100-69:100.
Preferably, in described step c, described substrate is polytetrafluoroethylene (PTFE).
Preferably, in described step c, described bake out temperature is 60-80 ℃.
Preferably, in described step c, described drying time is 1-6h.
Preferably, in described steps d, described ammoniacal liquor addition is 200-1000 μ L.
Preferably, in described steps d, described hydrothermal temperature is 140-180 ℃.
Preferably, in described steps d, the described hydro-thermal reaction time is 1-5h.
Preferably, in described steps d, also comprise hydro-thermal reaction is obtained nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/the cobaltosic oxide extrusion coating paper is by washed with de-ionized water and dry.
Beneficial effect of the present invention is as follows:
Method step provided by the invention is simple, it is simple and easy to operate, reaction condition is gentle, nitrogen-doped graphene/the nitrogen-doped carbon nanometer pipe of preparation/cobaltosic oxide extrusion coating paper is compared with nitrogen-doped graphene/cobaltosic oxide extrusion coating paper, there is the ORR catalytic performance of obvious enhancing, have a good application prospect in the electro-catalysis field.
The accompanying drawing explanation
The optical photograph of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 1 provides for the embodiment of the present invention 1/cobaltosic oxide extrusion coating paper;
The cross-sectional scans electron micrograph of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 2 provides for the embodiment of the present invention 1/cobaltosic oxide extrusion coating paper;
The outer surface electron scanning micrograph of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 3 provides for the embodiment of the present invention 1/cobaltosic oxide extrusion coating paper;
The high multiple cross-sectional scans electron micrograph of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 4 provides for the embodiment of the present invention 1/cobaltosic oxide extrusion coating paper;
The ORR curve of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 5 provides for the embodiment of the present invention 1/cobaltosic oxide extrusion coating paper.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, concrete technical scheme of the present invention is specifically described.
The invention provides the preparation method of a kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper, comprise the following steps:
A., the graphene oxide dispersion liquid is provided;
This step a specifically comprises the steps:
A1. by strong acid for example the concentrated sulfuric acid pour in the mixture of graphite scale and sodium nitrate, stir and to obtain dispersion liquid; The mass ratio of graphite scale and sodium nitrate is preferably 4:3.
A2. slowly add for example potassium permanganate of strong oxidizer in the a1 dispersion liquid, stir the 20h left and right, place 2-8 days, be preferably 5 days; The mass ratio of graphite scale and potassium permanganate is preferably 1:3-1:5.
A3. add successively deionized water and hydrogen peroxide in a2; Hydrogen peroxide is about 5:2 with the ratio of potassium permanganate amount of substance.
A4. obtain the graphene oxide dispersion liquid after many centrifuge washings, dialysis.
The concentration of the graphene oxide dispersion liquid in above-mentioned steps a is 1-6mg/mL, is preferably 2-4mg/mL.
B., the oxide/carbon nanometer tube dispersion liquid is provided;
This step b specifically comprises the steps:
B1. by strong acid for example the concentrated sulfuric acid pour in the mixture of CNT and sodium nitrate, stir and to obtain dispersion liquid; The mass ratio of CNT and sodium nitrate is preferably 4:3.
B2. slowly add for example potassium permanganate of strong oxidizer in the b1 dispersion liquid, stir 20-30h, be preferably the 24h left and right; The mass ratio of CNT and potassium permanganate is preferably 1:1-1:2.
B3. add successively deionized water and hydrogen peroxide in b2; Hydrogen peroxide is about 5:2 with the ratio of potassium permanganate amount of substance.
B4. obtain the oxide/carbon nanometer tube dispersion liquid after suction filtration, washing.
The concentration of the oxide/carbon nanometer tube dispersion liquid in above-mentioned steps b is 1-10mg/mL, is preferably 2-6mg/mL.
C. described graphene oxide dispersion liquid, oxide/carbon nanometer tube dispersion liquid and cobalt nitrate solution are mixed to get to slurry, then described slurry are coated on substrate, then dried to obtain the graphene oxide that comprises cobalt ions/oxide/carbon nanometer tube extrusion coating paper;
Preferably, the graphene oxide in above-mentioned steps c, oxide/carbon nanometer tube mass ratio are 15:1-5:1, more preferably 10:1.
Preferably, the graphene oxide in above-mentioned steps c and the mass ratio of cobalt nitrate are 17:100-69:100, more preferably 34:100.
Preferably, the bake out temperature in above-mentioned steps c is 60-80 ℃.
Preferably, the drying time in above-mentioned steps c is 1-6h.
In the optional step of above-mentioned steps c, the size and dimension of the graphene oxide that comprises cobalt ions made/oxide/carbon nanometer tube extrusion coating paper changes along with the change of polytetrafluoroethylsubstrate substrate.
D. the graphene oxide by will comprise cobalt ions/oxide/carbon nanometer tube extrusion coating paper immerses and carries out hydro-thermal reaction in the aqueous solution of ammonia and obtain described nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper.
Preferably, the hydrothermal temperature in above-mentioned steps d is 140-180 ℃, is preferably 180 ℃.
Preferably, the hydro-thermal reaction time in above-mentioned steps d is 1-5h, is preferably 2h.
Preferably, the ammoniacal liquor addition in above-mentioned steps d is 200-1000 μ L, is preferably 500 μ L.
The present invention be take graphene oxide, oxide/carbon nanometer tube, cobalt nitrate and ammoniacal liquor as raw material, under magnetic agitation, oxide/carbon nanometer tube dispersion liquid and cobalt nitrate solution dropwise added in the graphene oxide dispersion liquid successively, and due to electrostatic interaction, Co
2+to be adsorbed on electronegative graphene oxide and oxide/carbon nanometer tube surface.This mixture is coated on polytetrafluoroethylsubstrate substrate, is placed in drying in oven, along with the volatilization of moisture, graphene oxide and oxide/carbon nanometer tube complete self assembly, have formed the graphene oxide that comprises cobalt ions of self-supporting/oxide/carbon nanometer tube extrusion coating paper.Add appropriate amount of deionized water and ammoniacal liquor in autoclave, to comprise in the aqueous solution that the graphene oxide of cobalt ions/oxide/carbon nanometer tube extrusion coating paper immerses ammonia, the sealed high pressure reactor is placed in baking oven and carries out hydro-thermal reaction, in hydrothermal reaction process, graphene oxide, oxide/carbon nanometer tube are reduced and adulterate and enter the nitrogen element, simultaneously Co
2+original position generates the cobaltosic oxide nano particle, has obtained nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper.In nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper, the existence of nitrogen-doped carbon nanometer pipe can prevent that Graphene is stacking, increases the basal plane spacing, improves electric conductivity.
The invention has the advantages that simple to operate, reaction condition is gentle, prepare in large quantities nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper, this extrusion coating paper has good ORR electrocatalysis characteristic, in the electro-catalysis field, has a good application prospect.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe provided by the invention/cobaltosic oxide extrusion coating paper is described in detail.
Below in each embodiment each raw material be from the market and buy.
(1) preparation of graphene oxide dispersion liquid: take 5.0 gram graphite scales and 3.75 gram NaNO
3be placed in the beaker of 1 liter, open mechanical agitation, slowly add 150 milliliters of concentrated sulfuric acids (98%); After stirring half an hour, by 20 gram KMnO
4within half an hour, join in above-mentioned dispersion liquid; Continue stir about after 20 hours, because reactant viscosity increases, electric stirring lost efficacy, and stopped stirring; Place after 5 days (during artificial reaction stirred) once in a while, slowly add 500 ml deionized water (stirring of limit edged), the rear 30 milliliters of H that slowly add stir
2o
2, generate glassy yellow suspension; This suspension is centrifugal, remove supernatant, retain lower sediment, then precipitation is added to aqueous dispersion, this process triplicate, wash away the kish ion; Then, the precipitation of acquisition is added to aqueous dispersion, centrifugal, collect upper strata centrifugate, lower sediment is continued to add aqueous dispersion centrifugal, collect upper strata centrifugate; The upper strata centrifugate of collecting is merged, and the bag filter that is then 8000-14000 with molecular weight is dialysed, and the product of gained has been carried out to Raman Characterization, and it is positioned at 1350cm
-1d be less than it with the intensity of characteristic peak and be positioned at 1590cm
-1the G band characteristic peak at place, result shows to have obtained the graphene oxide uniform dispersion.
(2) preparation of oxide/carbon nanometer tube dispersion liquid: take 0.5 gram CNT and 0.375 gram NaNO
3be placed in the conical flask of 250 milliliters, open magnetic agitation, slowly add 15 milliliters of concentrated sulfuric acids (98%); After stirring half an hour, by 1 gram KMnO
4within half an hour, join in above-mentioned dispersion liquid; Continue stir about after 24 hours, slowly add successively 50 ml deionized water and 1.5 milliliters of H
2o
2, generate black suspension; By this suspension suction filtration, wash by deionized water; The oxide/carbon nanometer tube finally suction filtration obtained is dispersed in water, and obtains the uniform dispersion of oxide/carbon nanometer tube.
(3) after the graphene oxide dispersion liquid of 10 milliliter of 2 mg/ml is mixed with the oxide/carbon nanometer tube dispersion liquid of 1 milliliter of 2 mg/ml is even, the cobalt nitrate aqueous solution that adds 0.2 milliliter of 1 mol/L, after mixing, the slurry obtained is layered on polytetrafluoroethylsubstrate substrate, put into 80 ℃ of baking oven reactions after 2 hours, take out, be cooled to room temperature, obtain the graphene oxide that comprises cobalt ions/oxide/carbon nanometer tube extrusion coating paper.
(4) preparation of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper: add appropriate amount of deionized water and 500 μ L ammoniacal liquor in autoclave, the graphene oxide that comprises cobalt ions of tearing from substrate/oxide/carbon nanometer tube extrusion coating paper is immersed in the aqueous solution of ammonia, the sealed high pressure reactor also is placed in 180 ℃ of baking ovens, react after 2 hours, be cooled to room temperature, obtain nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper, use deionized water rinsing, dry, as shown in Figure 1.
Described nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper is carried out to the field emission scanning electron microscope observation, result is referring to Fig. 2, the cross-sectional scans electron micrograph of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 2 provides for the embodiment of the present invention 1/cobaltosic oxide extrusion coating paper, as shown in Figure 2, the thickness of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that the present invention obtains/cobaltosic oxide extrusion coating paper is about 4 μ m, and has orderly sandwich construction.The outer surface electron scanning micrograph of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 3 provides for the embodiment of the present invention 1/cobaltosic oxide extrusion coating paper, as shown in Figure 3, the extrusion coating paper Surface Creation cobaltosic oxide particle of about one deck diameter 100nm.The high multiple cross-sectional scans electron micrograph of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 4 provides for the present embodiment 1/cobaltosic oxide extrusion coating paper, as shown in Figure 4, there is the cobaltosic oxide particle of a large amount of nitrogen-doped carbon nanometer pipes and diameter 25nm between the nitrogen-doped graphene lamella.Described nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper is carried out to the test of ORR electrocatalysis characteristic, result is referring to Fig. 5, the ORR curve of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that Fig. 5 provides for this example 1/cobaltosic oxide extrusion coating paper, as shown in Figure 5, be about-0.06V of take-off potential, the current density at-0.9V place is-4.87mA cm
-2.The electron transfer number at calculate-0.7V place is 3.97, and kinetic limiting current density is 13.57mA cm
-2.Result shows, nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper has good ORR electrocatalysis characteristic, and its methanol tolerance performance and durability are better than business Pt/C eelctro-catalyst.
Embodiment 6
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper comprises the following steps:
A. prepare the graphene oxide dispersion liquid;
B. prepare the oxide/carbon nanometer tube dispersion liquid;
C. described graphene oxide dispersion liquid, oxide/carbon nanometer tube dispersion liquid are mixed to obtain slurry with cobalt nitrate solution, then described slurry is coated on substrate, then dried to obtain the graphene oxide that comprises cobalt ions/oxide/carbon nanometer tube extrusion coating paper;
D. the graphene oxide by will comprise cobalt ions/oxide/carbon nanometer tube extrusion coating paper immerses and carries out hydro-thermal reaction in the aqueous solution of ammonia and obtain described nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper.
2. preparation method according to claim 1, is characterized in that, described graphene oxide dispersion liquid provides by following steps:
A1. strong acid is poured in the mixture of graphite scale and nitrate, stirred and obtain dispersion liquid;
A2. add strong oxidizer in the described dispersion liquid of a1, stir, place a period of time, obtain the aubergine pastel;
A3. add successively deionized water and hydrogen peroxide in the described aubergine pastel of a2, obtain glassy yellow suspension;
A4. the described glassy yellow suspension of a3 is centrifugal, the washing and the dialysis, obtain described graphene oxide dispersion liquid.
3. preparation method according to claim 1, is characterized in that, the concentration of the graphene oxide dispersion liquid in described step a is 1-6mg/mL.
4. preparation method according to claim 1, is characterized in that, described oxide/carbon nanometer tube dispersion liquid provides by following steps:
B1. strong acid is poured in the mixture of CNT and nitrate, stirred and obtain dispersion liquid;
B2. add strong oxidizer in the described dispersion liquid of b1, stir, obtain the black pastel;
B3. add successively deionized water and hydrogen peroxide in the described black pastel of b2, obtain black suspension;
B4. by described black suspension suction filtration, the washing of b3, obtain described oxide/carbon nanometer tube dispersion liquid.
5. preparation method according to claim 1, is characterized in that, the concentration of the oxide/carbon nanometer tube dispersion liquid in described step b is 1-10mg/mL.
6. preparation method according to claim 1, is characterized in that, the graphene oxide in described step c, oxide/carbon nanometer tube mass ratio are 15:1-5:1; Graphene oxide in described step c and the mass ratio of cobalt nitrate are 17:100-69:100.
7. preparation method according to claim 1, is characterized in that, the substrate in described step c is polytetrafluoroethylene (PTFE); Described bake out temperature is 60-80 ℃; Described drying time is 1-6h.
8. preparation method according to claim 1, is characterized in that, the hydrothermal temperature in described steps d is 140-180 ℃; The hydro-thermal reaction time is 1-5h; Described ammoniacal liquor addition is 200-1000 μ L.
9. according to the described preparation method of claim 1 or 8, it is characterized in that, in described steps d, also comprise will hydro-thermal reaction be obtained nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/the cobaltosic oxide extrusion coating paper is by washed with de-ionized water and dry.
10. nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe that the described method of claim 1～9 any one prepares/cobaltosic oxide extrusion coating paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310390188.0A CN103480406B (en) | 2013-08-30 | 2013-08-30 | A kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310390188.0A CN103480406B (en) | 2013-08-30 | 2013-08-30 | A kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103480406A true CN103480406A (en) | 2014-01-01 |
| CN103480406B CN103480406B (en) | 2015-09-09 |
Family
ID=49821192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310390188.0A Expired - Fee Related CN103480406B (en) | 2013-08-30 | 2013-08-30 | A kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103480406B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762362A (en) * | 2016-05-23 | 2016-07-13 | 四川大学 | Carbon-coated ferroferric oxide/nitrogen-doped grapheme composite material and preparation method thereof |
| CN106229541A (en) * | 2016-07-27 | 2016-12-14 | 安徽师范大学 | A kind of N C/Co3o4hollow ball shaped nanometer material and its preparation method and application |
| CN106744838A (en) * | 2016-12-06 | 2017-05-31 | 武汉工程大学 | The method that one step hydro thermal method prepares N doping porous graphene |
| CN108039499A (en) * | 2017-10-23 | 2018-05-15 | 广东工业大学 | A kind of N doping peels off the preparation method of carbon nanotube loaded cobaltosic oxide material |
| CN108232213A (en) * | 2017-12-01 | 2018-06-29 | 复旦大学 | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof |
| CN108550862A (en) * | 2018-03-12 | 2018-09-18 | 华南理工大学 | A kind of cobaltosic oxide-amino carbon nanotube composite electro catalytic material and preparation and application |
| CN109844183A (en) * | 2016-09-14 | 2019-06-04 | 爱法组装材料公司 | The manufacture of graphene |
| CN109903998A (en) * | 2019-02-26 | 2019-06-18 | 内蒙古科技大学 | A kind of combination electrode and its preparation method and application |
| CN111211331A (en) * | 2020-01-10 | 2020-05-29 | 北京化工大学 | Method for improving performance of cathode of aluminum-air battery |
| CN113363504A (en) * | 2020-07-15 | 2021-09-07 | 河海大学 | Preparation method of platinum/manganese cobaltate nanocrystal/nitrogen-doped graphene three-dimensional composite electrode catalyst |
| CN114068970A (en) * | 2021-10-22 | 2022-02-18 | 复旦大学 | Photo-assisted lithium-carbon dioxide battery and preparation method thereof |
| CN114188617A (en) * | 2021-11-30 | 2022-03-15 | 河池市科学技术情报和创新服务所 | Production process of low-dimensional nano lead-carbon super battery |
| EP4174992A1 (en) * | 2021-10-26 | 2023-05-03 | National Kaohsiung University of Science and Technology | Cathode electrocatalyst for metal air batteries and production process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012100354A1 (en) * | 2011-01-28 | 2012-08-02 | Zhongwei Chen | Core-shell structured bifunctional catalysts for metal air battery/fuel cell |
| CN102849731A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nitrogen-doped graphene hydrogel, preparation method and applications thereof |
-
2013
- 2013-08-30 CN CN201310390188.0A patent/CN103480406B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012100354A1 (en) * | 2011-01-28 | 2012-08-02 | Zhongwei Chen | Core-shell structured bifunctional catalysts for metal air battery/fuel cell |
| CN102849731A (en) * | 2012-09-07 | 2013-01-02 | 中国科学技术大学 | Nitrogen-doped graphene hydrogel, preparation method and applications thereof |
Non-Patent Citations (2)
| Title |
|---|
| PING CHEN ET AL: ""A Nitrogen-Doped Graphene/Carbon Nanotube Nanocomposite with Synergistically Enhanced Electrochemical Activity"", 《ADVANCED MATERIALS》, 8 May 2013 (2013-05-08), pages 3192 - 3196 * |
| YONGYE LIANG ET AL: ""Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction"", 《NATURE MATERIALS》, vol. 10, 31 October 2011 (2011-10-31), pages 780 - 786, XP055068985, DOI: doi:10.1038/nmat3087 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762362B (en) * | 2016-05-23 | 2018-12-11 | 四川大学 | Carbon coated ferriferrous oxide/nitrogen-doped graphene composite material and its application and preparation |
| CN105762362A (en) * | 2016-05-23 | 2016-07-13 | 四川大学 | Carbon-coated ferroferric oxide/nitrogen-doped grapheme composite material and preparation method thereof |
| CN106229541A (en) * | 2016-07-27 | 2016-12-14 | 安徽师范大学 | A kind of N C/Co3o4hollow ball shaped nanometer material and its preparation method and application |
| CN106229541B (en) * | 2016-07-27 | 2019-06-25 | 安徽师范大学 | A kind of N-C/Co3O4Hollow ball shaped nanometer material and its preparation method and application |
| CN109844183A (en) * | 2016-09-14 | 2019-06-04 | 爱法组装材料公司 | The manufacture of graphene |
| CN106744838A (en) * | 2016-12-06 | 2017-05-31 | 武汉工程大学 | The method that one step hydro thermal method prepares N doping porous graphene |
| CN108039499B (en) * | 2017-10-23 | 2023-10-03 | 广东工业大学 | Preparation method of nitrogen-doped exfoliated carbon nanotube loaded cobaltosic oxide material |
| CN108039499A (en) * | 2017-10-23 | 2018-05-15 | 广东工业大学 | A kind of N doping peels off the preparation method of carbon nanotube loaded cobaltosic oxide material |
| CN108232213A (en) * | 2017-12-01 | 2018-06-29 | 复旦大学 | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof |
| CN108550862A (en) * | 2018-03-12 | 2018-09-18 | 华南理工大学 | A kind of cobaltosic oxide-amino carbon nanotube composite electro catalytic material and preparation and application |
| CN109903998A (en) * | 2019-02-26 | 2019-06-18 | 内蒙古科技大学 | A kind of combination electrode and its preparation method and application |
| CN111211331A (en) * | 2020-01-10 | 2020-05-29 | 北京化工大学 | Method for improving performance of cathode of aluminum-air battery |
| CN113363504A (en) * | 2020-07-15 | 2021-09-07 | 河海大学 | Preparation method of platinum/manganese cobaltate nanocrystal/nitrogen-doped graphene three-dimensional composite electrode catalyst |
| CN113363504B (en) * | 2020-07-15 | 2022-06-14 | 河海大学 | Preparation method of platinum/manganese cobaltate nanocrystal/nitrogen-doped graphene three-dimensional composite electrode catalyst |
| CN114068970A (en) * | 2021-10-22 | 2022-02-18 | 复旦大学 | Photo-assisted lithium-carbon dioxide battery and preparation method thereof |
| CN114068970B (en) * | 2021-10-22 | 2023-08-01 | 复旦大学 | Light-assisted lithium carbon dioxide battery and preparation method thereof |
| EP4174992A1 (en) * | 2021-10-26 | 2023-05-03 | National Kaohsiung University of Science and Technology | Cathode electrocatalyst for metal air batteries and production process thereof |
| JP7419331B2 (en) | 2021-10-26 | 2024-01-22 | 國立高雄科技大學 | Cathode catalyst for metal-air batteries and its manufacturing method |
| CN114188617A (en) * | 2021-11-30 | 2022-03-15 | 河池市科学技术情报和创新服务所 | Production process of low-dimensional nano lead-carbon super battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103480406B (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103480406B (en) | A kind of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobaltosic oxide extrusion coating paper and preparation method thereof | |
| CN105251513B (en) | The electro-deposition preparation method of carbon nanotube/transistion metal compound composite material | |
| Zhang et al. | Highly active and durable Pt/MXene nanocatalysts for ORR in both alkaline and acidic conditions | |
| CN107029772B (en) | Non-noble metal catalyst and preparation method thereof | |
| CN104616915B (en) | A kind of preparation method of graphene ruthenium-oxide composite | |
| CN104923204A (en) | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst | |
| Askari et al. | Construction of Co3O4-Ni3S4-rGO ternary hybrid as an efficient nanoelectrocatalyst for methanol and ethanol oxidation in alkaline media | |
| CN106025244A (en) | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof | |
| CN105719850A (en) | Grapheme@polypyrrole/layer double hydroxide nanowire ternary composite and preparation method and application thereof | |
| CN104659357A (en) | Supported nickel-iron composite hydroxide oxygen evolution electrode for alkaline water electrolysis and preparation method for supported nickel-iron composite hydroxide oxygen evolution electrode | |
| CN108232213A (en) | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof | |
| CN107335451A (en) | The preparation method of platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst | |
| CN111634954B (en) | Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof | |
| CN110124687A (en) | A kind of preparation method of the LDH/rGO composite material of ruthenium doping and its application on evolving hydrogen reaction | |
| CN107961793A (en) | Nickel cobalt oxyhydroxide adulterates the analysis oxygen catalysis material of graphene oxide | |
| CN105977501A (en) | High-performance oxygen reduction MnO2-Mn3O4/carbon nanotube composite catalyst and preparation method and application thereof | |
| CN104022291A (en) | Microbial fuel cell, cathode, cathode catalyst and preparation methods thereof | |
| Zhang et al. | Zirconium boride as a novel negative catalyst for vanadium redox flow battery | |
| CN104258848B (en) | Preparation method and application of Pt/3D (Three dimensional) graphene composite catalyst | |
| Li et al. | Bimetal-MOF and bacterial cellulose-derived three-dimensional N-doped carbon sheets loaded Co/CoFe nanoparticles wrapped graphite carbon supported on porous carbon nanofibers: An efficient multifunctional electrocatalyst for Zn-air batteries and overall water splitting | |
| CN105778088B (en) | A kind of graphene/polyaniline nanometer stick array composite and preparation method and application | |
| CN114100660A (en) | Titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst, and preparation method and application thereof | |
| CN108273524B (en) | Carbon composite material modified by chalcogenide and transition metal and preparation method and application thereof | |
| CN101814609B (en) | Anode composite catalyst Pt-HxMoO3 for direct methanol fuel cells, and preparation method thereof | |
| CN109734134B (en) | Preparation and application of coral-like structure ferroferric oxide nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150909 Termination date: 20210830 |