CN107482232A - A kind of fuel cell oxygen reduction electrocatalyst phosphorus, the preparation method of nitrogen co-doped carbon material - Google Patents
A kind of fuel cell oxygen reduction electrocatalyst phosphorus, the preparation method of nitrogen co-doped carbon material Download PDFInfo
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- CN107482232A CN107482232A CN201710741795.5A CN201710741795A CN107482232A CN 107482232 A CN107482232 A CN 107482232A CN 201710741795 A CN201710741795 A CN 201710741795A CN 107482232 A CN107482232 A CN 107482232A
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
The invention discloses the preparation method of a kind of fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen co-doped carbon material, melamine and pyrophosphoric acid are well mixed wiring solution-forming with deionized water through ultrasonic disperse, obtained solution is moved into microwave hydrothermal reaction kettle, 35min is reacted in microwave hydrothermal reaction under 150 DEG C, 380W microwave condition, obtained product is washed with deionized until filtrate becomes colorless, put into vacuum drying chamber and dried in 80 DEG C to constant weight, then in N24h is calcined in 700 DEG C obtain peanut shape constructed fuel cells oxygen reduction electro-catalyst phosphorus, nitrogen co-doped carbon material under atmosphere.Present invention incorporates the advantages of microwave unique heat characteristic and hydro-thermal method, there is the advantages of simple to operate, reproducible and reaction efficiency is high, be adapted to industrialized production and application.
Description
Technical field
The invention belongs to the preparing technical field of fuel-cell catalyst, and in particular to a kind of fuel cell oxygen reduction electricity is urged
The preparation method of agent phosphorus, nitrogen co-doped carbon material.
Background technology
Fuel cell technology is a kind of advanced energy technology, and it has, and energy conversion efficiency is high, environment-friendly and energy
The advantages that density is high.But the oxygen reduction reaction of fuel battery negative pole is slow, Cathodic oxygen reduction is to influence fuel cell electricity to urge
An important factor for changing reaction speed.Therefore, oxygen reduction catalyst is one of focus of fuel cell Study of electrocatalysis.
At present, the catalyst of the oxygen reduction reaction of fuel cell substantially uses Pt sills, because being currently known
In metal material, electro catalytic activity highest of the metal platinum to oxygen reduction reaction.To improve reaction rate and conversion efficiency, often need
Substantial amounts of platinum is wanted to be catalyzed the oxygen reduction reaction of acceleration negative electrode.Due to using the cost of platinum too high, fuel cell is seriously constrained
Development.Non-precious metal catalyst cheap, that oxygen reduction catalytic activity is high is researched and developed to urge to substitute the platinum base of main flow
Agent is the only way of fuel cell development.
Doping carbon-supported catalysts have the characteristics that oxygen reduction catalytic activity is high, stability is good, and low with cost of material
It is honest and clean, the advantages that wide material sources.Therefore, doping carbon-supported catalysts very likely substitute platinum based catalyst, there is good application prospect.
But carbon-supported catalysts often have obvious decay by longtime running its performance.Therefore, nano-sized carbon how is further improved to urge
The longtime running stability of agent is one of emphasis of elctro-catalyst research.
The content of the invention
Present invention solves the technical problem that it there is provided a kind of fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen co-doped carbon materials
The preparation method of material, the material has good hydrogen reduction electro catalytic activity, and the microwave hydrothermal preparation method used combines
The advantages of microwave unique heat characteristic and hydro-thermal method, there is the advantages of simple to operate, reproducible and reaction efficiency is high, fit
Close industrialized production and application.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of fuel cell oxygen reduction electrocatalyst
The preparation method of phosphorus, nitrogen co-doped carbon material, it is characterised in that concretely comprise the following steps：By melamine and pyrophosphoric acid and deionized water
Be well mixed wiring solution-forming through ultrasonic disperse, by obtained solution move into microwave hydrothermal reaction kettle in, 150 DEG C, 380W it is micro-
35min is reacted under the conditions of ripple in microwave hydrothermal reaction, obtained product is washed with deionized until filtrate is changed into nothing
Color, put into vacuum drying chamber and dried in 80 DEG C to constant weight, then in N24h is calcined in 700 DEG C obtain peanut shape structure under atmosphere
Fuel cell oxygen reduction electrocatalyst phosphorus, nitrogen co-doped carbon material.
Further preferably, the mass ratio that feeds intake of the melamine and pyrophosphoric acid is 1:1.
The present invention has the advantages that compared with prior art：
1st, the present invention successfully synthesizes the phosphorus with peanut shape structure, nitrogen co-doped carbon material first, and the special appearance structure has
Beneficial to the specific surface area for improving catalyst, increase the catalytic activity of elctro-catalyst；
2nd, the microwave-hydrothermal method that uses of the present invention combines the advantages of microwave unique heat characteristic and hydro-thermal method, simple to operate,
Reaction speed is fast, generated time is short, reaction condition is gentle and reaction efficiency is high；
3rd, new fuel cell catalyst produced by the present invention is compared with the nanocarbon catalyst of only N doping, such catalyst
With higher activity, the catalysis material surface that is doped to of phosphorus atoms creates more positively charged sites, enhances to oxygen
Molecular Adsorption, the pi-electron enriched in carbon conjugated system is activated, phosphorus, nitrogen have played the good cooperative effect to carbon material together.
Brief description of the drawings
Fig. 1 is the SEM figures that the embodiment of the present invention 1 prepares phosphorus, nitrogen co-doped carbon material；
Fig. 2 is the oxygen reduction reaction polarization curve of catalyst in the embodiment of the present invention 1 and comparative example 1, comparative example 2.
Fig. 3 be oxygen in the embodiment of the present invention 1 and comparative example 1, comparative example 2 before and after the accelerated life test of catalyst also
Former polarization curve.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
0.01g melamines and 0.01g pyrophosphoric acids are well mixed wiring solution-forming with 40mL deionized waters through ultrasonic disperse；Will
To solution move into 100mL microwave hydrothermal reaction kettle, in microwave hydrothermal reaction under 150 DEG C, 380W microwave condition
Middle reaction 35min；By obtained product be washed with deionized until filtrate become colorless, put into vacuum drying chamber in 80
DEG C dry to constant weight, then in N24h are calcined in 700 DEG C obtain dye cell oxygen reduction electro-catalyst phosphorus, nitrogen co-doped under atmosphere
Carbon material.
Phosphorus, nitrogen co-doped carbon material made from the present embodiment are peanut shape structure as seen from Figure 1, this special material
Material composition and appearance structure are advantageous to improve the specific surface area of catalyst, are effectively increased the catalytic activity of elctro-catalyst.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.It is respectively 1cm to electrode and reference electrode to scribble the glass-carbon electrode of catalyst as working electrode2's
The saturated calomel electrode of platinized platinum and Ag/AgCl, electrolyte are the 0.1M KOH aqueous solution.To make catalyst be attached to glass-carbon electrode
On, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation process of thin layer catalyst is as follows on electrode：Take 5mg
The perfluorinated sulfonic acid that catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse about 10min, use are micro-
Amount injector takes 15 μ L to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode, can be surveyed after being dried at room temperature for
Examination, electric performance test result is as shown in Figure 2 and Figure 3.
Comparative example 1
0.01g melamines and 0.05g mass concentrations are mixed for 37% formalin with 40mL deionized waters through ultrasonic disperse
Uniform wiring solution-forming；Obtained solution is transferred in autoclave and sealed, 6h is reacted in 180 DEG C, reaction is natural after terminating
It is cooled to room temperature；By obtained product be washed with deionized until filtrate become colorless, put into vacuum drying chamber in 80 DEG C
Dry to constant weight, then in N22h is calcined in 800 DEG C obtain nitrogen-doped carbon material fuel cell catalyst under atmosphere.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.It is respectively 1cm to electrode and reference electrode to scribble the glass-carbon electrode of catalyst as working electrode2's
The saturated calomel electrode of platinized platinum and Ag/AgCl, electrolyte are the 0.1M KOH aqueous solution.To make catalyst be attached to glass-carbon electrode
On, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation process of thin layer catalyst is as follows on electrode：Take 5mg
The perfluorinated sulfonic acid that catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse about 10min, use are micro-
Amount injector takes 15 μ L to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode, can be surveyed after being dried at room temperature for
Examination, electric performance test result is as shown in Figure 2 and Figure 3.
Comparative example 2
Take 20% Pt/Xc-72 of JM companies of the business platinum catalyst U.S..
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.It is respectively 1cm to electrode and reference electrode to scribble the glass-carbon electrode of catalyst as working electrode2's
The saturated calomel electrode of platinized platinum and Ag/AgCl, electrolyte are the 0.1M KOH aqueous solution.To make catalyst be attached to glass-carbon electrode
On, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation process of thin layer catalyst is as follows on electrode：Take 5mg
The perfluorinated sulfonic acid that catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse about 10min, use are micro-
Amount injector takes 15 μ L to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode, can be surveyed after being dried at room temperature for
Examination, electric performance test result is as shown in Figure 2 and Figure 3.
Fuel-cell catalyst obtained by the present invention has good hydrogen reduction electro catalytic activity and stability.It is comprehensive real
Apply example 1 and comparative example 1-2, it can be seen that the phosphorus of preparation, nitrogen co-doped carbon material peanut shape structure（Fig. 1）；Electric performance test knot
Fruit（Fig. 2,3）In, curve a is respectively the polarization curve and stability of catalyst prepared by embodiment 1 in Fig. 2, Fig. 3, and b, c distinguish
The polarization curve and stability of catalyst prepared by corresponding comparative example 2, comparative example 1, compared with comparative example 1-2, prepared by embodiment 1
Catalyst carrying current and take-off potential it is maximum, stability is best, shows that the catalyst shows highest electro-chemical activity
And stability；We think there is the specific surface area that the special appearance structure of peanut shape is advantageous to improve catalyst, increase
The catalytic activity of elctro-catalyst, the catalysis material surface that is doped to of phosphorus atoms create more positively charged sites, enhanced
Oxygen molecule is adsorbed, has activated the pi-electron enriched in carbon conjugated system, phosphorus, nitrogen have played the good collaboration to carbon material together
Effect, show the electro catalytic activity excellent performance of fuel-cell catalyst produced by the present invention, be before one kind has wide application
The fuel-cell catalyst of scape.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. a kind of fuel cell oxygen reduction electrocatalyst phosphorus, the preparation method of nitrogen co-doped carbon material, it is characterised in that specific step
Suddenly it is：Melamine and pyrophosphoric acid are well mixed wiring solution-forming through ultrasonic disperse with deionized water, obtained solution is moved into
In microwave hydrothermal reaction kettle, 35min is reacted in microwave hydrothermal reaction under 150 DEG C, 380W microwave condition, will be obtained
Product be washed with deionized until filtrate becomes colorless, put into vacuum drying chamber and dried in 80 DEG C to constant weight, Ran Hou
N24h is calcined in 700 DEG C obtain peanut shape constructed fuel cells oxygen reduction electro-catalyst phosphorus, nitrogen co-doped carbon material under atmosphere.
2. fuel cell oxygen reduction electrocatalyst phosphorus according to claim 1, the preparation method of nitrogen co-doped carbon material, its
It is characterised by：The mass ratio that feeds intake of the melamine and pyrophosphoric acid is 1:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111834640A (en) * | 2019-04-15 | 2020-10-27 | 武汉氢阳能源有限公司 | Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof |
| CN116072891A (en) * | 2022-12-07 | 2023-05-05 | 成都先进金属材料产业技术研究院股份有限公司 | Method for obtaining N, P co-doped graphite felt electrode |
Citations (3)
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| CN102765712A (en) * | 2012-07-09 | 2012-11-07 | 陕西科技大学 | Method for preparing carbon microspheres |
| CN103794803A (en) * | 2014-01-22 | 2014-05-14 | 江西师范大学 | Preparation method and application of nitrogen-phosphorus co-doped carbon-oxygen reduction catalyst for microbial fuel cell |
| CN105924174A (en) * | 2016-04-26 | 2016-09-07 | 武汉大学 | Preparation method of carbon-based composite material |
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2017
- 2017-08-25 CN CN201710741795.5A patent/CN107482232A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765712A (en) * | 2012-07-09 | 2012-11-07 | 陕西科技大学 | Method for preparing carbon microspheres |
| CN103794803A (en) * | 2014-01-22 | 2014-05-14 | 江西师范大学 | Preparation method and application of nitrogen-phosphorus co-doped carbon-oxygen reduction catalyst for microbial fuel cell |
| CN105924174A (en) * | 2016-04-26 | 2016-09-07 | 武汉大学 | Preparation method of carbon-based composite material |
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| PHILIPPE SERP，ET AL.: "《Nanostructured Carbon Materials for Catalysis》", 2 March 2015 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111834640A (en) * | 2019-04-15 | 2020-10-27 | 武汉氢阳能源有限公司 | Efficient and stable organic matter electrocatalytic oxidation catalyst and preparation method and application thereof |
| CN116072891A (en) * | 2022-12-07 | 2023-05-05 | 成都先进金属材料产业技术研究院股份有限公司 | Method for obtaining N, P co-doped graphite felt electrode |
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Application publication date: 20171215 |