CN107317042A - Microwave-hydrothermal method prepares sulphur, nitrogen, the method for iron codope carbon material fuel battery negative pole elctro-catalyst - Google Patents
Microwave-hydrothermal method prepares sulphur, nitrogen, the method for iron codope carbon material fuel battery negative pole elctro-catalyst Download PDFInfo
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- CN107317042A CN107317042A CN201710741277.3A CN201710741277A CN107317042A CN 107317042 A CN107317042 A CN 107317042A CN 201710741277 A CN201710741277 A CN 201710741277A CN 107317042 A CN107317042 A CN 107317042A
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- microwave
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- carbon material
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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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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
- H01M4/96—Carbon-based electrodes
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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
Abstract
Sulphur is prepared the invention discloses a kind of microwave-hydrothermal method, nitrogen, the method of iron codope carbon material fuel battery negative pole elctro-catalyst, by 2 amino 1, 3, 5 triazines 4, 6 two mercaptan and mass concentration are well mixed wiring solution-forming with deionized water for 37% formalin through ultrasonic disperse, add iron chloride and be uniformly mixed and obtain suspension, obtained suspension is moved into microwave hydrothermal reaction kettle, at 140 DEG C, 30min is reacted in microwave hydrothermal reaction under 400W 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 N23h is calcined in 800 DEG C obtain sulphur, nitrogen, iron codope carbon material fuel battery negative pole elctro-catalyst under atmosphere.Present invention incorporates the unique heat characteristic of microwave and the advantage of hydro-thermal method, have the advantages that 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 microwave-hydrothermal method prepare sulphur,
The method of nitrogen, iron codope carbon material fuel battery negative pole elctro-catalyst.
Background technology
Fuel cell technology is a kind of advanced energy technology, and it has energy conversion efficiency high, environment-friendly and energy
The advantages of density is high.But the oxygen reduction reaction of fuel battery negative pole is slow, Cathodic oxygen reduction is that influence fuel cell electricity is urged
Change the key factor of 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 too high using the cost of platinum, fuel cell is seriously constrained
Development.The high non-precious metal catalyst of cheap, oxygen reduction catalytic activity is researched and developed to urge to substitute the platinum base of main flow
Agent is the only way of fuel cell development.
Influence the factor of non-precious metal catalyst activity a lot, such as the microscopic appearance and state, reactant of catalyst surface
With mass transfer characteristic of the product in catalysis material etc..The microscopic appearance and state and preparation method of wherein catalyst are closely related,
Using different preparation methods, the pattern state of catalyst is very different, so as to be produced a very large impact to catalyst activity.
Due to special form, unique chemical composition, the nano material with yolk eggshell structure shows huge in every field
Application potential, its abundant hole can also promote mass transfer and electro transfer, and then improve the activity of catalyst.
The content of the invention
Present invention solves the technical problem that there is provided a kind of microwave-hydrothermal method prepares sulphur, nitrogen, the combustion of iron codope carbon material
Expect the method for cell cathode elctro-catalyst, sulphur, nitrogen, iron codope carbon material made from this method have good fuel cell cloudy
Pole hydrogen reduction electro catalytic activity, combines the advantage of the unique heat characteristic of microwave and hydro-thermal method, with simple to operate, repeatability
The good and high advantage of reaction efficiency, is adapted to industrialized production and application.
The present invention adopts the following technical scheme that microwave-hydrothermal method prepares sulphur, nitrogen, iron codope to solve above-mentioned technical problem
The method of carbon material fuel battery negative pole elctro-catalyst, it is characterised in that concretely comprise the following steps：By 2- amino -1,3,5- triazine -4,
The mercaptan of 6- bis- and mass concentration are well mixed wiring solution-forming with deionized water for 37% formalin through ultrasonic disperse, add
Iron chloride is simultaneously uniformly mixed and obtains suspension, and obtained suspension is moved into microwave hydrothermal reaction kettle, 140 DEG C,
30min is reacted in microwave hydrothermal reaction under 400W microwave condition, obtained product is washed with deionized until filtering
Liquid becomes colorless, and puts into vacuum drying chamber and is dried in 80 DEG C to constant weight, then in N23h is calcined under atmosphere in 800 DEG C to obtain
Sulphur, nitrogen, iron codope carbon material fuel battery negative pole elctro-catalyst.
Further preferably, the 2- amino-mercaptan of 1,3,5-triazines -4,6- bis-, mass concentration for 37% formalin with
The mass ratio that feeds intake of iron chloride is 1:6:10.
The present invention has the advantages that compared with prior art：
1st, the present invention successfully synthesizes the sulphur with yolk eggshell structure, nitrogen, iron codope carbon material first, and the hollow structure can
To provide three-phase for electrode reaction（Solid-liquid-gas）Area, provides passage, and then improve the ratio table of catalyst for the transmission of electrolyte
Area, increases the catalytic activity of elctro-catalyst；
2nd, present invention incorporates the unique heat characteristic of microwave and the advantage of hydro-thermal method, simple to operate, reaction speed is fast, synthesis when
Between short, reaction condition it 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 sulphur atom creates more positively charged sites, enhances to oxygen
Molecular Adsorption, has activated the pi-electron enriched in carbon conjugated system, and sulphur, nitrogen, iron have played the good collaboration effect to carbon material together
Should.
Brief description of the drawings
Fig. 1 is the TEM figures that fuel battery negative pole elctro-catalyst is made in embodiment 1；
Fig. 2 is the Cathodic oxygen reduction polarization curve of catalyst in embodiment 1 and comparative example 1 and comparative example 2.
Embodiment
The above to 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
Formalin and 40mL by the mercaptan of 0.01g 2- amino -1,3,5- triazines -4,6- two and 0.06g mass concentrations for 37%
Deionized water is well mixed wiring solution-forming through ultrasonic disperse, adds 0.1g iron chloride and is uniformly mixed and obtains suspension；
In the microwave hydrothermal reaction kettle that obtained suspension is moved into 100mL, in microwave hydrothermal under 140 DEG C, 400W microwave condition
30min is reacted in reaction instrument；Obtained product is washed with deionized up to filtrate becomes colorless, put to vacuum drying chamber
In in 80 DEG C dry to constant weight, then in N23h is calcined in 800 DEG C obtain sulphur, nitrogen, iron codope carbon material fuel electricity under atmosphere
Pool cathode elctro-catalyst.
Sulphur, nitrogen, iron codope carbon material made from the present embodiment are yolk eggshell structure, this spy as seen from Figure 1
Different material composition and appearance structure provides passage for the transmission of electrolyte, and then improves the specific surface area of catalyst, effectively increases
The catalytic activity of electrocatalyst.
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 is 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, with 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.
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, adds 0.1g iron chloride and is uniformly mixed and obtain suspension；Obtained suspension is transferred to height
Press in reactor and seal, 6h is reacted in 180 DEG C, reaction naturally cools to room temperature after terminating；By obtained product deionized water
Washing becomes colorless up to filtrate, puts into vacuum drying chamber and is dried in 80 DEG C to constant weight, then in N2Forged under atmosphere in 800 DEG C
Burn 2h and obtain nitrogen, iron codope carbon material fuel-cell 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 is 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, with 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.
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 is 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, with 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.
Fuel-cell catalyst produced by the present invention has good hydrogen reduction electro catalytic activity.Integrated embodiment 1 and right
Ratio 1-2, it can be seen that sulphur, nitrogen, the iron codope carbon material of preparation are yolk eggshell structure（Fig. 1）；Electric performance test result
（Fig. 2）In, curve a be embodiment 1 prepare catalyst electrical property, b, c respectively correspond to comparative example 2, comparative example 1 prepare urge
The electrical property of agent, compared with comparative example 1-2, catalyst carrying current made from embodiment 1 and half wave potential are maximum, illustrate oxygen
Reduce electro catalytic activity highest；We think that the hollow structure with yolk eggshell can provide three-phase for electrode reaction
（Solid-liquid-gas）Area, passage is provided for the transmission of electrolyte, and then improves the specific surface area of catalyst, increase elctro-catalyst
Catalytic activity, while the catalysis material surface that is doped to of sulphur atom creates more positively charged sites, is enhanced to oxygen
Son absorption, has activated the pi-electron enriched in carbon conjugated system.Sulphur, nitrogen, iron have played the good collaboration effect to carbon material together
Should, show the electro catalytic activity excellent performance of fuel-cell catalyst produced by the present invention, be that one kind has broad prospect of application
Fuel-cell catalyst.
Embodiment above describes general principle, principal character and the advantage of the present invention, 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. microwave-hydrothermal method prepares sulphur, nitrogen, the method for iron codope carbon material fuel battery negative pole elctro-catalyst, it is characterised in that
Concretely comprise the following steps：By the formalin and deionized water that the mercaptan of 2- amino -1,3,5- triazines -4,6- two and mass concentration are 37%
Wiring solution-forming is well mixed through ultrasonic disperse, iron chloride is added and is uniformly mixed and obtain suspension, it is suspended by what is obtained
Liquid is moved into microwave hydrothermal reaction kettle, and 30min is reacted in microwave hydrothermal reaction under 140 DEG C, 400W microwave condition, will
Obtained product is washed with deionized until filtrate becomes colorless, and puts into vacuum drying chamber and is dried in 80 DEG C to constant weight, so
Afterwards in N23h is calcined in 800 DEG C obtain sulphur, nitrogen, iron codope carbon material fuel battery negative pole elctro-catalyst under atmosphere.
2. microwave-hydrothermal method according to claim 1 prepares sulphur, nitrogen, iron codope carbon material fuel battery negative pole electro-catalysis
The method of agent, it is characterised in that：The mercaptan of 2- amino -1,3,5- triazines -4,6- two, mass concentration are 37% formalin
The mass ratio that feeds intake with iron chloride is 1:6:10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112234213A (en) * | 2020-09-24 | 2021-01-15 | 江苏理工学院 | Preparation method and application of transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst |
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| CN1708869A (en) * | 2002-10-31 | 2005-12-14 | 松下电器产业株式会社 | Porous electrode, and electrochemical element made using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112234213A (en) * | 2020-09-24 | 2021-01-15 | 江苏理工学院 | Preparation method and application of transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst |
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Application publication date: 20171103 |