CN103928688A - Method for preparing oxygen precipitation electrode based on three-dimensional porous graphene - Google Patents
Method for preparing oxygen precipitation electrode based on three-dimensional porous graphene Download PDFInfo
- Publication number
- CN103928688A CN103928688A CN201410155737.0A CN201410155737A CN103928688A CN 103928688 A CN103928688 A CN 103928688A CN 201410155737 A CN201410155737 A CN 201410155737A CN 103928688 A CN103928688 A CN 103928688A
- Authority
- CN
- China
- Prior art keywords
- dimensional porous
- electrode
- graphite oxide
- porous graphene
- oxygen
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for preparing oxygen precipitation electrode based on three-dimensional porous grapheme. The method includes the following steps: 1) oxidizing graphite powder to prepare a graphite oxide; 2) carrying out vacuum drying on the graphite oxide prepared in step 1) at 60-80 DEG C; 3) carrying out heat treatment on the dried graphite oxide prepared in step 2) in vacuum at 80-120 DEG C for 8-24 hours; 4) heating the graphite oxide in step 3) in vacuum to 180-250 DEG C in vacuum and keeping for 5-60 minutes. The oxygen precipitation electrode based on three-dimensional porous grapheme prepared by the method disclosed by the invention has excellent catalytic performance of oxygen precipitation and good long term stability, can be used for replacing costly iridium and an oxide electrode thereof, is widely applied in fields such as photocatalytic water splitting and metal-air battery as well as other energy source converting devices, and has a high practical value, and the raw material of the oxygen precipitation electrode disclosed by the invention is common graphite powder, so that the oxygen precipitation electrode is wide in raw material source, low in cost, simple in preparation method and suitable for mass production.
Description
Technical field
The present invention relates to a kind of oxygen and separate out the preparation method of electrode, be specifically related to a kind of oxygen based on three-dimensional porous Graphene and separate out the preparation method of electrode.
Background technology
The evolution reaction of oxygen is one of most important electrocatalytic reaction, is widely used in the fields such as photodissociation water and metal-air battery.Iridium and oxide electrode thereof are that the traditional electrode of current oxygen evolution reaction is also the most frequently used electrode, but iridium is as noble metal, its expensive, resource-constrained, and performance loss is serious during long-play, has hindered the commercialized development in the fields such as photodissociation water and metal-air battery.The wretched insufficiency such as when, resource-constrained expensive for iridium and oxide electrode thereof, long-play performance loss is serious, Recent study finds that some transition metal (for example manganese and nickel) oxide material shows certain oxygen and separates out performance, but transition metal oxide oxygen Evolution overpotential is conventionally higher, effect is undesirable, and complex steps, is difficult to realize large-scale production.For example:
a Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles. Jin Suntivich et al. Science 334,1383 (2011). DOI:10.1126/science.1212858; Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis. Rodney D. L. Smith et al. Science 340,60 (2013). DOI:10.1126/science.1233638; Photochemical Water Oxidation by Crystalline Polymorphs of Manganese Oxides:Structural Requirements for Catalysis. David M. Robinson et al. J. Am. Chem. Soc. 135,3494 (2013). DOI:10.1021/ja310286h.
Therefore, study a kind of efficient, low price, reliable and stable, the simple oxygen of preparation process is separated out electrode and is seemed very necessary.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of oxygen based on three-dimensional porous Graphene to separate out the preparation method of electrode, this electrode has good oxygen and separates out catalytic performance and long-time stability, and raw material source is abundant, preparation method is simple, cheap.
For achieving the above object, the invention provides following technical scheme:
Oxygen based on three-dimensional porous Graphene of the present invention is separated out the preparation method of electrode, comprises the following steps:
1) graphite powder is oxidized and prepares graphite oxide;
2) graphite oxide of being prepared by step 1) vacuumize at 60 ~ 80 ℃;
3) by step 2) dried graphite oxide 80 ~ 120 ℃ of heat treatment 8 ~ 24h under vacuum of obtaining;
4) graphite oxide in step 3) is warming up under vacuum to 180 ~ 250 ℃ and keep 5 ~ 60min, the oxygen that the product obtaining is based on three-dimensional porous Graphene is separated out electrode.
Further, in described step 1), use the concentrated sulfuric acid, sodium nitrate and potassium permanganate that graphite powder is oxidized, prepare graphite oxide.
Further, described step 2) in, more than graphite oxide vacuumize 10h.
Further, in described step 3), dried graphite oxide is pulverized or is cut into small pieces, and then heat-treat.
Further, in described step 4), graphite oxide is rapidly heated with the speed higher than 1 ℃/s under the condition of 0.03Pa at low vacuum.
Beneficial effect of the present invention is:
The present invention prepares graphite oxide by graphite oxidation, then graphite oxide is carried out to a series of vacuumize and vacuum heat, the oxygen of preparing based on three-dimensional porous Graphene is separated out electrode, the experiment proved that, this electrode has good oxygen and separates out catalytic performance and long-time stability, and raw material of the present invention is common graphite powder, raw material sources are extensive, cheap, preparation method simple, be applicable to large-scale production.
Graphene is a kind of new material of the individual layer laminated structure consisting of carbon atom, is a kind ofly by carbon atom, with sp2 hybridized orbit, to form the flat film that hexangle type is honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Since the physicist An Deliehaimu of Univ Manchester UK in 2004 and Constantine Nuo Woxiaoluofu successfully isolate Graphene in experiment from graphite, Graphene, because of its good conductivity, light transmission and flex capability having, makes it in fields such as touch-screen, liquid crystal display, organic photovoltaic battery, Organic Light Emitting Diodes, as transparent electrical conductive electrode, be widely used.And having efficient oxygen, the three-dimensional porous Graphene of being prepared by method of the present invention separates out catalytic performance, can be used as oxygen and separate out electrode use, thereby expanded the range of application of Graphene, oxygen based on three-dimensional porous Graphene prepared by the present invention is separated out iridium and the oxide electrode thereof of the alternative costliness of electrode, and be widely used in the fields such as photodissociation water and metal-air battery and other energy conversion apparatus, possess higher practical value.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearer, the invention provides following accompanying drawing and describe:
Fig. 1 is the scanning electron microscope (SEM) photograph of the three-dimensional porous Graphene electrodes of embodiment 1 preparation;
Fig. 2 is three-dimensional porous Graphene electrodes and the polarization curve comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation;
Fig. 3 is three-dimensional porous Graphene electrodes and the stability comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation;
Fig. 4 is the scanning electron microscope (SEM) photograph of the three-dimensional porous Graphene electrodes of embodiment 2 preparations;
Fig. 5 is three-dimensional porous Graphene electrodes and the polarization curve comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations;
Fig. 6 is three-dimensional porous Graphene electrodes and the stability comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1
The oxygen based on three-dimensional porous Graphene of the present embodiment is separated out the preparation method of electrode, comprises the following steps:
1) use the concentrated sulfuric acid, sodium nitrate and potassium permanganate that graphite powder is oxidized, prepare graphite oxide;
2) graphite oxide of being prepared by step 1) is vacuumize 20h at 80 ℃;
3) by step 2) the dried graphite oxide that obtains pulverizes, 100 ℃ of heat treatment 12h under vacuum then;
4) graphite oxide in step 3) is about to the speed with 2 ℃/s under 0.0088Pa condition in vacuum degree and is rapidly heated to 200 ℃ and keeps 10min, the oxygen that the product obtaining is based on three-dimensional porous Graphene is separated out electrode.
Fig. 1 is the scanning electron microscope (SEM) photograph of the three-dimensional porous Graphene electrodes of embodiment 1 preparation; From figure, can find out clearly three-dimensional and there is the Graphene of loose structure.
Fig. 2 is three-dimensional porous Graphene electrodes and the polarization curve comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation, find to compare with yttrium oxide/carbon electrode, three-dimensional porous Graphene electrodes shows more negative take-off potential, illustrates that three-dimensional porous Graphene electrodes has efficient oxygen and separates out catalytic performance.
Fig. 3 is three-dimensional porous Graphene electrodes and the stability comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 1 preparation, find to compare with yttrium oxide/carbon electrode, after operation 3000s, three-dimensional porous Graphene electrodes has more negative current potential 1.50V, than yttrium oxide/carbon electrode current potential, improved about 29mV, illustrate that three-dimensional porous Graphene electrodes is more suitable for long-term operation, has higher stability.
Above-mentioned experimental data shows, the three-dimensional porous Graphene electrodes of embodiment 1 preparation has good oxygen and separates out catalytic performance and long-time stability, and the iridium of alternative costliness and oxide electrode thereof are separated out electrode as oxygen and used.
embodiment 2
The oxygen based on three-dimensional porous Graphene of the present embodiment is separated out the preparation method of electrode, comprises the following steps:
1) use the concentrated sulfuric acid, sodium nitrate and potassium permanganate that graphite powder is oxidized, prepare graphite oxide;
2) graphite oxide of being prepared by step 1) is vacuumize 24h at 60 ℃;
3) by step 2) the dried graphite oxide that obtains pulverizes, 80 ℃ of heat treatment 16h under vacuum then;
4) graphite oxide in step 3) is about to the speed with 3 ℃/s under 0.012Pa condition in vacuum degree and is rapidly heated to 180 ℃ and keeps 30min, the oxygen that the product obtaining is based on three-dimensional porous Graphene is separated out electrode.
Fig. 4 is the scanning electron microscope (SEM) photograph of the three-dimensional porous Graphene electrodes of embodiment 2 preparations; From figure, can find out clearly three-dimensional and there is the Graphene of loose structure.
Fig. 5 is three-dimensional porous Graphene electrodes and the polarization curve comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations, find to compare with yttrium oxide/carbon electrode, three-dimensional porous Graphene electrodes shows more negative take-off potential, illustrates that three-dimensional porous Graphene electrodes has efficient oxygen and separates out catalytic performance.
Fig. 6 is three-dimensional porous Graphene electrodes and the stability comparison diagram of yttrium oxide/carbon electrode in the saturated 0.1M KOH of oxygen solution of embodiment 2 preparations, find to compare with yttrium oxide/carbon electrode, after operation 3500s, three-dimensional porous Graphene electrodes has more negative current potential 1.49V, than yttrium oxide/carbon electrode current potential, improved about 27mV, illustrate that three-dimensional porous Graphene electrodes is more suitable for long-term operation, has higher stability.
Above-mentioned experimental data shows, the three-dimensional porous Graphene electrodes of embodiment 2 preparations has good oxygen and separates out catalytic performance and long-time stability, and the iridium of alternative costliness and oxide electrode thereof are separated out electrode as oxygen and used.
Finally explanation is, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can to it, make various changes in the form and details, and not depart from the claims in the present invention book limited range.
Claims (5)
1. the oxygen based on three-dimensional porous Graphene is separated out the preparation method of electrode, it is characterized in that: comprise the following steps:
1) graphite powder is oxidized and prepares graphite oxide;
2) graphite oxide of being prepared by step 1) vacuumize at 60 ~ 80 ℃;
3) by step 2) dried graphite oxide 80 ~ 120 ℃ of heat treatment 8 ~ 24h under vacuum of obtaining;
4) graphite oxide in step 3) is warming up under vacuum to 180 ~ 250 ℃ and keep 5 ~ 60min, the oxygen that the product obtaining is based on three-dimensional porous Graphene is separated out electrode.
2. the oxygen based on three-dimensional porous Graphene according to claim 1 is separated out the preparation method of electrode, it is characterized in that: in described step 1), use the concentrated sulfuric acid, sodium nitrate and potassium permanganate that graphite powder is oxidized, prepare graphite oxide.
3. the oxygen based on three-dimensional porous Graphene according to claim 1 is separated out the preparation method of electrode, it is characterized in that: described step 2), more than graphite oxide vacuumize 10h.
4. the oxygen based on three-dimensional porous Graphene according to claim 1 is separated out the preparation method of electrode, it is characterized in that: in described step 3), dried graphite oxide is pulverized or is cut into small pieces, and then heat-treat.
5. the oxygen based on three-dimensional porous Graphene according to claim 1 is separated out the preparation method of electrode, it is characterized in that: in described step 4), graphite oxide is rapidly heated with the speed higher than 1 ℃/s under the condition of 0.03Pa at low vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410155737.0A CN103928688B (en) | 2014-04-18 | 2014-04-18 | Oxygen based on three-dimensional porous Graphene separates out the preparation method of electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410155737.0A CN103928688B (en) | 2014-04-18 | 2014-04-18 | Oxygen based on three-dimensional porous Graphene separates out the preparation method of electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103928688A true CN103928688A (en) | 2014-07-16 |
| CN103928688B CN103928688B (en) | 2016-03-30 |
Family
ID=51146829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410155737.0A Expired - Fee Related CN103928688B (en) | 2014-04-18 | 2014-04-18 | Oxygen based on three-dimensional porous Graphene separates out the preparation method of electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103928688B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107868A (en) * | 2011-03-01 | 2011-06-29 | 哈尔滨工程大学 | Method for preparing porous graphene material |
| CN102646839A (en) * | 2012-03-30 | 2012-08-22 | 中国科学院青岛生物能源与过程研究所 | Carbon material and carbon composite material used for air electrode of lithium air battery |
| US20130283603A1 (en) * | 2011-08-29 | 2013-10-31 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing positive electrode active material for lithium ion battery |
| CN103466604A (en) * | 2013-08-13 | 2013-12-25 | 华东理工大学 | Preparation method of porous graphene |
-
2014
- 2014-04-18 CN CN201410155737.0A patent/CN103928688B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107868A (en) * | 2011-03-01 | 2011-06-29 | 哈尔滨工程大学 | Method for preparing porous graphene material |
| US20130283603A1 (en) * | 2011-08-29 | 2013-10-31 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing positive electrode active material for lithium ion battery |
| CN102646839A (en) * | 2012-03-30 | 2012-08-22 | 中国科学院青岛生物能源与过程研究所 | Carbon material and carbon composite material used for air electrode of lithium air battery |
| CN103466604A (en) * | 2013-08-13 | 2013-12-25 | 华东理工大学 | Preparation method of porous graphene |
Non-Patent Citations (1)
| Title |
|---|
| CHUN XIAN GUO，ET AL.: "DNA-Functionalized Graphene to Guide Growth of Highly Active Pd Nanocrystals as Effi cient Electrocatalyst for Direct Formic Acid Fuel Cells", 《ADV. ENERGY MATER.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103928688B (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101289389B1 (en) | Method of Manufacturing Graphene using Electronic Decomposition | |
| CN102544479B (en) | Preparation method of zinc cobaltate array/carbon cloth composite anode material of lithium ion battery | |
| CN107570190B (en) | Preparation method of carbon-doped carbon nitride film electrode | |
| CN102923697A (en) | Method for preparing graphene energy storing material through electrochemical cathodic disbonding | |
| Hao et al. | Efficient light harvesting and charge collection of dye-sensitized solar cells with (001) faceted single crystalline anatase nanoparticles | |
| CN109850892B (en) | Twice-activation industrial preparation method of high-conductivity coconut shell activated carbon for super capacitor | |
| CN103924261B (en) | Oxygen based on reduced graphene oxide serving separates out the preparation method of electrode | |
| CN104944392A (en) | Mass preparation method of graphite-phase carbon nitride nanosheets | |
| CN102181877A (en) | Graphene oxide for electrochemical reduction and preparation method of graphene | |
| CN104108709A (en) | Porous graphene and preparation method thereof | |
| CN104117391B (en) | A kind of photoelectrocatalysis film preparation for hydrogen production by water decomposition | |
| CN104129781B (en) | A kind of situ Nitrogen Doping porous graphene and preparation method thereof | |
| CN102220615A (en) | Method for preparing CdS/ZnO nanotube array photoelectrode | |
| CN103132120A (en) | Method for preparing photoelectrocatalysis electrode material capable of efficiently degrading organic pollutants | |
| CN112707386A (en) | Preparation method and application of waste biomass derived graphene material | |
| CN104944418A (en) | Single-step method for preparing doped graphene with adjustable nitrogen content and adjustable varieties in situ | |
| CN106206043A (en) | A kind of FeS2nanometer rods/Graphene is to electrode material and preparation method and application | |
| CN103700513A (en) | Graphene paper and preparation method and application thereof | |
| CN103474243A (en) | Preparation method for dye-sensitized solar cell counter electrode based on nickel sulfide nanosheets | |
| CN106637285B (en) | Cu2The TiO 2 nanotubes modified optoelectronic pole of O quantum dot and its preparation and application | |
| CN112958116A (en) | Bi2O2.33-CdS composite photocatalyst and preparation process thereof | |
| CN106744835A (en) | A kind of method that utilization maize straw prepares Graphene | |
| CN111589457A (en) | Photocatalytic material for in-situ growth of three-dimensional copper sulfide on copper mesh, preparation method and application | |
| CN111286752B (en) | Nitrogen-doped graphite phase carbon nitride nanosheet/molybdenum disulfide composite material and preparation method thereof | |
| CN106906487B (en) | A kind of method that carbon dioxide by photoelectric catalytic reduction prepares ethyl alcohol |
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 |
Granted publication date: 20160330 Termination date: 20180418 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |