CN108448120A - Fe/PIL/MWCNTs fuel-cell catalysts and preparation method thereof - Google Patents
Fe/PIL/MWCNTs fuel-cell catalysts and preparation method thereof Download PDFInfo
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- CN108448120A CN108448120A CN201810205138.3A CN201810205138A CN108448120A CN 108448120 A CN108448120 A CN 108448120A CN 201810205138 A CN201810205138 A CN 201810205138A CN 108448120 A CN108448120 A CN 108448120A
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
Fe/PIL/MWCNTs fuel-cell catalysts and preparation method thereof, belong to fuel cell catalyst technical field.By a certain amount of after poly- (1 vinyl imidazole of the bromination) ion liquid dissolving of polymerization preparation is in ethyl alcohol, the multi-walled carbon nanotube that acidification is crossed is added and is stirred dispersion, above-mentioned dispersion liquid then is added dropwise in the ferric nitrate ethanol solution prepared, certain time is stirred under certain temperature, by centrifugation, washing and dry obtained Fe/PIL/MWCNTs catalyst precarsors；Precursor is sent into tube furnace, under the nitrogen of certain flow rate, after high temperature pyrolysis after a period of time, by products therefrom in dilute nitric acid solution pickling processes, be filtered, washed and dried to obtain Fe/PIL/MWCNTs catalyst.Preparation method of the present invention is simple, and the catalyst of preparation has higher catalytic activity and stability, is with a wide range of applications in fuel cell field.
Description
Technical field
The present invention relates to the preparations of non-platinum fuel cells elctro-catalyst, and in particular to Fe/PIL/MWCNTs catalyst
Preparation method belongs to fuel cell catalyst technical field.
Background technology
Proton Exchange Membrane Fuel Cells is as a kind of very important novel sustainable alternative energy source, because of its transformation efficiency
High, the advantages that pollution is small, noise is low, environmental-friendly, easy to carry, it is considered to be solve current environmental pollution and energy crisis
One of main path.The principal element for influencing proton exchange film fuel battery performance is the redox reactions of cathode.Traditionally,
Catalyst material application as redox reactions it is most be platinum-base material, platinum-base material catalyst is in acid and alkaline item
All there is higher catalytic performance, but platinum is noble metal under part, resource is few, of high cost, to make Proton Exchange Membrane Fuel Cells
Cost greatly improve, in addition to this, the series of challenges such as also selective low and durability difference of platinum based catalyst.Therefore, more
Countless scholars is dedicated to finding high efficiency, low cost and sufficiently stable non-platinum metal material catalyst over year.However, although
There are many work of this respect, for there are also good achievements, but non-platinum catalyst compares business platinum carbon catalyst, in oxygen
Larger gap is remained in reduction reaction catalytic activity and stability, therefore, is continued to improve the non-carbon-based electricity of platinum nitrating and be urged
The preparation method of agent finds new nitrating source and modification, is lived with reducing the cost of the carbon-based elctro-catalyst of nitrating, improving its catalysis
Property and stability are still the research emphasis in the field.
Invention content
The present invention is intended to provide the preparation of a kind of simple for process, high catalytic activity and the fuel cell electro-catalyst of stability
Method especially makes the catalyst being prepared have good catalytic performance in acid condition.
The present invention is achieved by the following technical solutions, and the present invention includes the following steps：
The first step, the acidification oxidation processes of carbon nanotube；
Oil bath heating is carried out to the multi-walled carbon nanotube being put into concentrated nitric acid first, wherein it is preferred that multi-walled carbon nanotube g:It is dense
Nitric acid mL is 1:100, reaction temperature is controlled at 118 DEG C, and then reaction was completed, is obtained after supercooling, filtering and washing preliminary
The multi-walled carbon nanotube of processing；Secondly, above-mentioned multi-walled carbon nanotube is put into oil bath in concentrated hydrochloric acid, wherein it is preferred that multi-wall carbon nano-tube
Pipe g:Concentrated hydrochloric acid mL is 1:100, reaction temperature is controlled at 105 DEG C, and then reaction was completed, through supercooling, is filtered, is washed to neutrality
And the dry multi-walled carbon nanotube (MWCNTs) to acidification oxidation processes.
Second step, the preparation of bromination 1- vinyl iminazole ionic liquid monomers；
1- vinyl imidazoles, bromoethane and acetonitrile are added in three mouthfuls of reaction bulbs, is put into 70 DEG C of oil bath pan, in nitrogen
It is heated at reflux under atmosphere for 24 hours, after reaction, the ether for pouring into sufficient amount is extracted and made to unreacted raw material and solvent
Ionic liquid monomer precipitates, and precipitation is sent into the drying of 50 DEG C of vacuum drying chambers after filtering, obtain bromination 1- vinyl imidazoles from
Sub- liquid monomer.
Third walks, the synthesis of poly- bromination 1- vinyl iminazole ionic liquids (PIL)；
Bromination 1- vinyl iminazole ionic liquids in second step are dissolved in chloroform, polymerization initiator azo two is added
Isobutyronitrile is simultaneously back to few 3h under 70 DEG C of nitrogen atmospheres, is filtered to product and is washed off unreacted raw material with chloroform and polymerize and drawn
After sending out agent, product is dry, grinding obtains PIL powder；
4th step, the synthesis of Fe/PIL/MWCNTs precursor powders；
The poly- bromination 1- vinyl iminazole ionic liquids (PIL) that will be prepared in the MWCNTs prepared in the first step and third step
It is added in absolute ethyl alcohol to mixed liquor stably dispersing, then in addition prepares the ethanol solution of ferric nitrate, the ferric nitrate that will be prepared
Ethanol solution, which is added dropwise in above-mentioned gained mixed liquor, stirs 12h, and centrifugation, alcohol are washed, dry, ground, and Fe/PIL/ is obtained
MWCNTs precursors；
The mass ratio of MWCNTs and PIL is preferably 1:(3.75-15).
5th step, the synthesis of Fe/PIL/MWCNTs；
The Fe/PIL/MWCNTs precursor powders prepared in step 4 are put into progress high temperature in the tube furnace of logical nitrogen to forge
It burns, cooled to room temperature obtains final elctro-catalyst.
It is preferred that high-temperature calcination：Logical nitrogen drains the air in tube furnace before heating, is then heated up with the rate of 5 DEG C/min
To 100 DEG C, continue to stop heating after being warming up to 500-900 DEG C with 5 DEG C/min after maintaining a period of time, it is natural in nitrogen atmosphere
It is cooled to room temperature.
It is preferred that the mass percentage of Fe elements is 0.2%-0.6% in final products Fe/PIL/MWCNTs.
PIL and monomer are reacted by common oil bath to be prepared, and method is simple, the used time is short, by selection with not homonymy
The imidazoles of chain and the salt of different anions, so that it may to synthesize the PIL with the combination of different zwitterions, and in subsequent catalysis
Before agent in production procedure, MWCNTs, PIL and metal ion can be combined together, made only by simple stirring
It is standby simple, it is easy reproduction.
The present invention provides a kind of new non-platinum fuel cells catalyst, have expanded the type of fuel-cell catalyst, and
And the fuel-cell catalyst performance that the method for the present invention obtains is good.Compared to same type with ionic liquid or polymeric ionic liquid
As the non-platinum fuel cells cathod catalyst of nitrogen source, this method for preparing catalyst is simple, low raw-material cost, acid condition
The current density of lower catalytic oxidation-reduction is up to 1.0-2.0mA/cm2, initial reduction current potential is up to 0.80V, with extensive research
And application prospect, and highest also only has the take-off potential of 0.86V or so, acid item under other catalyst alkaline conditions of same type
Even more rare report or current potential are less than 0.7V under part.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic spectrogram of bromination 1- vinyl iminazole ionic liquid monomers；
Fig. 2 is Fe/PIL/MWCNTs catalyst ns prepared by embodiment 11SSpectrum analysis.Wherein a is oxidized form nitrogen peak, and b is
Graphite ene-type nitrogen peak, c are pyrroles's type nitrogen peak, and the peak value of d is pyridine type nitrogen peak.
Fig. 3 is the LSV figures of the Fe/PIL/MWCNTs catalyst precarsors that are prepared in embodiment 1 under different calcination temperatures；
Fig. 4 is the LSV figures of Fe/PIL/MWCNTs catalyst under the different nitrogen contents prepared in embodiment 1.
Fig. 5 is stability test.
Specific implementation mode
With reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
(1) it takes 1g multi-walled carbon nanotubes to be placed in 250mL three-necked flasks, pours into 100mL concentrated nitric acids and under the conditions of 118 DEG C
Pickling 6h is down to room temperature and filters, filtered carbon nanotube is placed into 250mL three-necked flasks, is poured into after reaction
100mL concentrated hydrochloric acids and pickling 6h under the conditions of 105 DEG C, are down to room temperature and filter after reaction, be then washed with deionized water to
Neutrality dries the multi-walled carbon nanotube to get acidification in 50 DEG C of vacuum drying chamber.
(2) to equipped with nitrogen valve, magneton, condenser pipe 100mL there-necked flasks in be added 9.00g 1- vinyl imidazoles,
28.88g bromoethanes and 50mL acetonitriles, under the conditions of nitrogen protection and 70 DEG C oil bath for 24 hours, solution is gone to immediately after reaction
In beaker and a certain amount of ether to solution is added there is white solid precipitation, filters simultaneously washed 3 times with ether later, it finally will be white
The product of color is put at 50 DEG C and is dried in vacuo to get to bromination 1- vinyl iminazole ionic liquid monomers.
(3) to equipped with nitrogen valve, magneton, condenser pipe 100mL there-necked flasks in be added the above-mentioned ionic liquid monomers of 3.00g and
30mL chloroforms, oil bath 3h under the conditions of nitrogen protection and 70 DEG C, are filtered after reaction, and chloroform is used in combination to precipitate 3 times, precipitation
It is put at 50 DEG C and is dried in vacuo to get to poly- bromination 1- vinyl iminazole ionic liquids.
(4) the PIL 3g in MWCNTs 0.4g and step (3) in step (1) are added in 250mL there-necked flasks, and add
Enter 60mL ethyl alcohol and carry out dispersing and dissolving, separately takes 2.98g Fe (NO3)3·9H2O is dissolved in the second that ferric nitrate is made in 50mL ethyl alcohol
This solution is then instilled in the mixed liquor in there-necked flask, reacts 12h under room temperature by alcoholic solution, then to product centrifugation, alcohol
It washes and dries 8h in 50 DEG C of vacuum drying chambers, pulverize to get Fe/PIL/MWCNTs catalyst precarsors.
(5) catalyst precarsor in step (4) is put into tube furnace and is pyrolyzed, logical N before heating up2By the air in tube furnace
It drains, is then first warming up to 100 DEG C with the rate of 5 DEG C/min, continue to be warming up to respectively with the rate of 5 DEG C/min after maintaining 1h
500, stop heating after 600,700,800,900 DEG C, in N2Cooled to room temperature in atmosphere obtains final elctro-catalyst.
Embodiment 2
(1) step leads to embodiment 1
(2) step leads to embodiment 1
(3) step leads to embodiment 1
(4) respectively with mass ratio 1:3.75、1:7.5、1:11.25、1:Step is added in 250mL there-necked flasks in 15 ratio
(1) wherein the MWCNTs in each ratio is 0.4g, and the progress of 60mL ethyl alcohol is added in the PIL in MWCNTs and step (3) in
Dispersing and dissolving separately takes 2.98g Fe (NO3) 39H2O to be dissolved in the ethanol solution that ferric nitrate is made in 50mL ethyl alcohol, then will
This solution instills in the mixed liquor in there-necked flask, reacts 12h under room temperature, is then washed to product centrifugation, alcohol and true at 50 DEG C
Dry 8h, pulverizes to get the Fe/PIL/MWCNTs catalyst precarsors of different nitrogen contents in empty drying box.
(5) catalyst precarsor in step (4) is put into tube furnace and is pyrolyzed, logical N before heating up2By the air in tube furnace
It drains, is then first warming up to 100 DEG C with the rate of 5 DEG C/min, continue to be warming up to 800 DEG C with the rate of 5 DEG C/min after maintaining 1h
Stop heating afterwards, in N2Cooled to room temperature in atmosphere obtains final elctro-catalyst.
Fig. 1 is the nuclear magnetic spectrum of bromination 1- vinyl iminazole ionic liquid monomers, is distributed and counts in conjunction with the hydrogen atom on figure
We have successfully synthesized this ionic liquid monomer known to calculating.
Fig. 2 is the N of Fe/PIL/MWCNTs catalyst prepared by embodiment 11sSpectrum analysis.Wherein a is oxidisability nitrogen peak,
I.e. bonding is the nitrogen of N-0 keys, and b is graphite ene-type nitrogen, i.e., the nitrogen being connected with three carbon atoms in class graphene-structured, c is pyrroles
Type nitrogen, represents the nitrogen being connected with two carbon atoms in five-membered ring, and d is to be connected with two carbon atoms in pyridine type nitrogen, that is, hexatomic ring
The appearance of nitrogen, wherein tri- peak b, c, d means the formation of C-N, and then demonstrates the key of MWCNTs and PIL in building-up process
It closes.
Fig. 3 is the LSV figures of the Fe/PIL/MWCNTs catalyst precarsors that are prepared in embodiment 1 under different calcination temperatures, from
It can be seen that Fe/PIL/MWCNTs catalyst precarsors are after high-temperature calcination on figure, take-off potential is greatly improved,
The catalytic performance highest wherein under 800 DEG C of calcination temperature is 0.1M HClO in electrolyte4, rotor speed 1600rpm, scanning
Under conditions of rate 10mV/s, take-off potential 0.80V, current density 1.6mA/cm2。
Fig. 4 is the Fe/PIL/MWCNTs catalyst precarsors LSV figures of the different nitrogen contents prepared in embodiment 2, can from figure
To find out the accounting variation with MWCNTs and PIL in the catalyst, initial reduction current potential and limiting current density also phase not to the utmost
Together, catalytic activity shows the trend of reduction after first increasing, the wherein best matter of catalytic activity with the doping ratio increase of PIL
It is MWCNTs to measure ratio:PIL=1:7.
Fig. 5 is best pyrolysis temperature and MWCNTs determined by embodiment 1 and embodiment 2:Under the conditions of PIL optimum quality ratios
Current stability is tested when the Fe/PIL/MWCNTs catalyst gauges of preparation, as can be seen from the figure in the starting stage of test,
The current density of Fe/PIL/MWCNTs catalyst and business Pt20%/C catalyst is all dramatic decrease, but after 3000s
Current density tends towards stability, and the current density of two kinds of catalyst is substantially the same, and illustrates the catalyst prepared by the present invention
Its stability already keeps abreast with business Pt20%/C catalyst.
Claims (9)
1. a kind of preparation method of fuel-cell catalyst, which is characterized in that include the following steps：
The first step, the acidification oxidation processes of carbon nanotube；
Second step, the preparation of bromination 1- vinyl iminazole ionic liquid monomers；
Third walks, the synthesis of poly- bromination 1- vinyl iminazole ionic liquids (PIL)；
4th step, the synthesis of Fe/PIL/MWCNTs precursor powders；
The poly- bromination 1- vinyl iminazole ionic liquids (PIL) prepared in the MWCNTs prepared in the first step and third step are added
To, to mixed liquor stably dispersing, then in addition preparing the ethanol solution of ferric nitrate in absolute ethyl alcohol, the ferric nitrate ethyl alcohol that will be prepared
Solution is added dropwise in above-mentioned gained mixed liquor and stirs, and centrifugation, alcohol are washed, dry, ground, and Fe/PIL/MWCNTs precursors are obtained；
5th step, the synthesis of Fe/PIL/MWCNTs；
The Fe/PIL/MWCNTs precursor powders prepared in step 4 are put into the tube furnace of logical nitrogen and carry out high-temperature calcination, from
It is so cooled to room temperature, obtains final elctro-catalyst.
2. a kind of preparation method of fuel-cell catalyst described in accordance with the claim 1, which is characterized in that the acid of carbon nanotube
Change oxidation processes specifically include as follows：Oil bath heating is carried out to the multi-walled carbon nanotube being put into concentrated nitric acid first, wherein it is preferred that
Multi-walled carbon nanotube g:Concentrated nitric acid mL is 1:100, reaction temperature is controlled at 118 DEG C, and then reaction was completed, through supercooling, filtering
With the multi-walled carbon nanotube for obtaining preliminary treatment after washing；Secondly, above-mentioned multi-walled carbon nanotube is put into oil bath in concentrated hydrochloric acid,
In preferably multi-walled carbon nanotube g:Concentrated hydrochloric acid mL is 1:100, reaction temperature is controlled at 105 DEG C, and then reaction was completed, through supercooling
But it, filters, be washed to the neutral and dry multi-walled carbon nanotube (MWCNTs) to acidification oxidation processes.
3. a kind of preparation method of fuel-cell catalyst described in accordance with the claim 1, which is characterized in that bromination 1- vinyl
The preparation of imidazole ion liquid monomer：1- vinyl imidazoles, bromoethane and acetonitrile are added in three mouthfuls of reaction bulbs, is put into 70 DEG C
In oil bath pan, be heated at reflux under nitrogen atmosphere for 24 hours, after reaction, pour into the ether of sufficient amount to unreacted raw material and
Solvent is extracted and ionic liquid monomer is made to precipitate, and precipitation is sent into 50 DEG C of vacuum drying chamber dryings after filtering, obtains bromine
Change 1- vinyl iminazole ionic liquid monomers.
4. a kind of preparation method of fuel-cell catalyst described in accordance with the claim 1, which is characterized in that poly- bromination 1- ethylene
The synthesis of base imidazole ion liquid (PIL)：Bromination 1- vinyl iminazole ionic liquids in second step are dissolved in chloroform, are added
Enter polymerization initiator azodiisobutyronitrile and be back to few 3h under 70 DEG C of nitrogen atmospheres, product is filtered and is washed off not with chloroform
After the raw material and polymerization initiator of reaction, product is dry, grinding obtains PIL powder.
5. a kind of preparation method of fuel-cell catalyst described in accordance with the claim 1, which is characterized in that stirred in the 4th step
At least 12h.
6. a kind of preparation method of fuel-cell catalyst described in accordance with the claim 1, which is characterized in that in the 4th step
The mass ratio of MWCNTs and PIL is 1:(3.75-15).
7. a kind of preparation method of fuel-cell catalyst described in accordance with the claim 1, which is characterized in that the 5th step high temperature
Calcining：Logical nitrogen drains the air in tube furnace before heating, is then warming up to 100 DEG C with the rate of 5 DEG C/min, maintains one section
Continue to stop heating, the cooled to room temperature in nitrogen atmosphere after being warming up to 500-900 DEG C with 5 DEG C/min after time.
8. a kind of preparation method of fuel-cell catalyst described in accordance with the claim 1, which is characterized in that final products Fe/
The mass percentage of Fe elements is 0.2%-0.6% in PIL/MWCNTs.
9. the fuel-cell catalyst being prepared according to any one of claim 1-8 methods.
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Cited By (2)
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| CN111584891A (en) * | 2020-05-21 | 2020-08-25 | 南通大学 | Atomic-level iron active site catalyst and preparation method and application thereof |
| CN113299929A (en) * | 2021-03-03 | 2021-08-24 | 昆明理工大学 | Preparation method of F, S, N co-doped Fe-N-C fuel cell oxygen reduction catalyst |
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| CN113299929A (en) * | 2021-03-03 | 2021-08-24 | 昆明理工大学 | Preparation method of F, S, N co-doped Fe-N-C fuel cell oxygen reduction catalyst |
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Application publication date: 20180824 |