CN106549166A - The carrier and its preparation method of the electrode catalyst of one proton exchanging film fuel battery - Google Patents
The carrier and its preparation method of the electrode catalyst of one proton exchanging film fuel battery Download PDFInfo
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- CN106549166A CN106549166A CN201611118005.XA CN201611118005A CN106549166A CN 106549166 A CN106549166 A CN 106549166A CN 201611118005 A CN201611118005 A CN 201611118005A CN 106549166 A CN106549166 A CN 106549166A
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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
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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
The invention discloses the carrier of the electrode catalyst of a proton exchanging film fuel battery, during the carrier supported catalyst for solve conventional carriers preparation technology complex operation, preparing, easily hinder the service efficiency of catalyst, easily cause the problem of catalyst poisoning, the carrier is by Graphene and allyl glycidyl ether, H2SnCl6With 4, after 4 diphthalic anhydrides are reacted respectively, product is reacted, carrier solution is obtained with graphite oxide alkene reaction finally.The carrier of the electrode catalyst of a proton exchanging film fuel battery proposed by the present invention, has good affinity to catalyst, with good conducting effect, the catalysis activity of catalyst can effectively be improved, its preparation technology is simple to operate, and preparation cost is low, is worthy to be popularized.
Description
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells technical field, more particularly to a proton exchanging film fuel battery
The carrier and its preparation method of electrode catalyst.
Background technology
Pem fuel fuel cell（PEMFC）As its operating temperature is relatively low, start fast, electroless liquid loss,
With the specific power higher than other fuel cells, not only stationary electric power plant can be made but also the power supply of destination can have been made, be expected to into
To replace the most competitive dynamic origin of current automobile power.At present, the existing London in the whole world, Canada temperature brother
Many countries and cities such as China, Stuttgart, Germany are proposed the bus line of fuel cell-driven, and many countries show
The fuel-cell vehicle of trial operation.China is also successfully proposed fuel cell-driven during Beijing Olympic Games and Shanghai World's Fair
Bus and car, there is now more than 1000 cars in national more than 10 city trial operation.As fuel cell is matched somebody with somebody
It is arranged the Fast Construction for applying hydrogenation stations, it will there are more fuel-cell vehicles to put into operation.According to Britain FuelCellToday and
U.S.'s Fuel Cells industry statistics, the growth that fuel cell installed capacity in 2012 was achieved at double compared with 2011.So
And which also has a certain distance, mainly high cost from commercial applications, key technology is not well solved.
The key technology of PEMFC mainly has PEM, elctro-catalyst, module loading electrode（MEA）, in the sensitivity and water pipe of CO
And heat management.Wherein, film assembling electrode is the core that guarantee electrochemical reaction efficiently can be carried out, by anode（Fuel electrode）, matter
Proton exchange and negative electrode（Oxygen electrode）Hot pressing is formed, and membrane electrode prepare it is critical only that control elctro-catalyst slurry proportioning with
Coating technique.
Fuel-cell catalyst carrier should possess good electronics (or proton) conducting power, larger specific surface area, close
The pore structure of reason and excellent corrosion resistance.The carrier for using on fuel cell at present is mainly high-graphitized carbon and carries
Body.But carbon carrier is weak with the interaction of noble metal catalyst, carbon carrier holds corrosion-prone problem, has a strong impact on catalyst
Activity and stability.Therefore, cheap stable novel carriers are developed significant.Number of patent application is
200680029098.7 electro-catalyst carriers for disclosing fuel cell, using a kind of cavernous dioxy doped with niobium element
Change titanium (otherwise referred to as " titanium dioxide (titania) ") as platinum or the high surface area of other suitable catalyst
Carrier, which has the characteristic suitable for PEM fuel cell environments, including appropriate surface area, electrical conductivity and chemically stable
Property, but its conducting effect is general, can only be simple play supported catalyst, the catalytic performance and catalytic efficiency to catalyst
Without facilitation, and there is the uppity shortcoming of preparation process；Number of patent application discloses fuel for 200680015088.8
The carrier of cell catalyst, is made up of at least one in titanium carbide and titanium oxide, for load comprising platinum or the conjunction containing platinum
The catalyst of the noble metals such as gold, during fuel cell use, can hinder the service efficiency of noble metal catalyst, and easily make
Into catalyst poisoning.Based on the problems referred to above, the present invention proposes the load of the electrode catalyst of a proton exchanging film fuel battery
Body and its preparation method.
The content of the invention
For above-mentioned situation, the purpose to overcome the defect of prior art, the present invention is just to provide a kind of PEM
The carrier of the electrode catalyst of fuel cell, it is therefore intended that the carrier for solve conventional carriers preparation technology complex operation, preparing is born
During carried catalyst, easily hinder the service efficiency of catalyst, easily cause the problem of catalyst poisoning.
The carrier of the electrode catalyst of one proton exchanging film fuel battery, the carrier is by Graphene and allyl glycidyl
Glycerin ether, H2SnCl6After being reacted with 4,4- diphthalic anhydrides respectively, product is reacted, finally with oxidation
Graphite alkene reaction is obtained carrier solution.
The preparation method of the carrier of the electrode catalyst of one proton exchanging film fuel battery, comprises the following steps：
S1, Graphene and allyl glycidyl ether reaction are obtained into Graphene complexation ether；
S2, by H2SnCl6Phthalic acid stannum is obtained with the reaction of 4,4- diphthalic anhydrides；
S3, by Graphene complexation ether and phthalic acid stannum reaction be obtained support powder；
S4, support powder and graphite oxide alkene reaction are obtained into carrier solution.
Preferably, step S1 in the preparation method is specially：In mass ratio 1:2.8～4.3 ratio, by Graphene
Stirring and dissolving is warming up to 80～90 DEG C in deionized water, is slowly added to NaOH solution and allyl glycidyl ether, side successively
Side stirring is added, after the completion of reaction, room temperature is cooled to, is separated out with excess ethyl alcohol and is precipitated, and be washed with deionized twice, removed
Unreacted allyl glycidyl ether, drying obtain Graphene complexation ether.
Preferably, the concentration of the NaOH solution is 2mol/L, and addition is 0.3～0.5 times of Graphene amount, the alkene
0.12～0.25 times for Graphene amount of the addition of propyl glycidyl ether.
Preferably, step S2 in the preparation method is specially：In mass ratio 1:4.5～5.5 ratio, by H2SnCl6
It is dissolved in DMSO solvents, oil bath is warming up to 76～88 DEG C, adds to dimethylamino naphthyridine, after 0.6～1h of reaction, add 4,
4- diphthalic anhydrides, after 1.2～2h of reaction, are cooled to room temperature, separate out precipitation with enough ethyl acetate, and washed with ethanol
Wash twice, remove unreacted impurity, drying obtains phthalic acid stannum.
Preferably, the addition to dimethylamino naphthyridine is H2SnCl60.4～0.6 times of amount, 4, the 4- bis- is adjacent
The addition of phthalate anhydride is H2SnCl60.9～1.2 times of amount.
Preferably, step S3 in the preparation method is specially：In mass ratio 1:5.8～6.25：5.5～6.5 ratio
Example, Graphene complexation ether and α-methacrylic acid are dissolved in toluene, add phthalic acid stannum, ethyleneglycol dimethacrylate
Ester and AIBN, after 30～50min of stirring at normal temperature, are heated to 58～68 DEG C in an oscillator, and ultrasonic vibration dissolves 1～2h, obtains white
Color is precipitated, and the support powder that particle diameter is 0.1～10 μm is ground to after sucking filtration, drying.
Preferably, 0.78～0.92 times for Graphene complexation ether amount of the addition of the phthalic acid stannum, the second
1.35～1.82 times for Graphene complexation ether amount of the addition of diol dimethacrylate.
Preferably, 0.09～0.13 times for Graphene complexation ether amount of the addition of the AIBN.
Preferably, step S4 in the preparation method is specially：In mass ratio 1～1.2:4.6～5.5 ratio, will
Support powder is dissolved in ethylene glycol, is warming up to 60～75 DEG C, the graphene oxide of excessive addition in there-necked flask, stirring reaction
0.4～0.6h is stood after 1～1.5h, carrier solution is filtered to obtain, the surface for being coated onto electrode forms graphene oxide monocrystalline
Layer carrier.
The carrier of the electrode catalyst of a proton exchanging film fuel battery proposed by the present invention, has to catalyst good
Affinity, with good conducting effect, prepare the graphene oxide single crystalline layer carrier for being formed and can effectively improve catalysis
The catalysis activity and utilization ratio of agent, does not result in catalyst poisoning phenomenon, the invention allows for a kind of combustion of PEM
The preparation method of the carrier of the electrode catalyst of material battery, by Graphene and allyl glycidyl ether, H2SnCl6And 4,4-
After diphthalic anhydrides are reacted respectively, product is reacted, carrier is obtained with graphite oxide alkene reaction finally
Solution, its preparation technology are simple to operate, and preparation cost is low, are adapted to industrialized production, are worthy to be popularized.
Description of the drawings
Monocell performance map when Fig. 1 is the carrier supported catalyst prepared using the embodiment of the present invention 1；
Monocell performance map when Fig. 2 is the carrier supported catalyst prepared using the embodiment of the present invention 2；
Monocell performance map when Fig. 3 is the carrier supported catalyst prepared using the embodiment of the present invention 3；
Monocell performance map when Fig. 4 is the carrier supported catalyst prepared using the embodiment of the present invention 4；
Monocell performance map when Fig. 5 is the carrier supported catalyst prepared using the embodiment of the present invention 5.
Specific embodiment
The present invention is further explained with reference to specific embodiment.
Embodiment one
The carrier of the electrode catalyst of a proton exchanging film fuel battery proposed by the present invention, the carrier is by Graphene and alkene
Propyl glycidyl ether, H2SnCl6After being reacted with 4,4- diphthalic anhydrides respectively, product is reacted, most
Carrier solution is obtained with graphite oxide alkene reaction afterwards.
Its preparation method, specifically includes following steps：
S1, by 30g Graphenes stirring and dissolving in 100ml deionized waters, be warming up to 82 DEG C, be slowly added to the concentration of 10ml successively
For the allyl glycidyl ether of the NaOH solution and 5ml of 2mol/L, stir while adding, after the completion of reaction, be cooled to room temperature,
Separated out with excess ethyl alcohol and precipitated, and be washed with deionized twice, remove unreacted allyl glycidyl ether, drying is obtained
Graphene complexation ether；
S2, by the H of 10g2SnCl6Be dissolved in the DMSO solvents of 50ml, oil bath is warming up to 80 DEG C, add 5ml to diformazan ammonia
Yl pyridines, after reaction 0.8h, add 4, the 4- diphthalic anhydrides of 10ml, after reaction 1.6h, are cooled to room temperature, with enough
Ethyl acetate separate out precipitation, and with washing with alcohol twice, remove unreacted impurity, drying obtains phthalic acid stannum；
S3, the α-methacrylic acid of 8.4g Graphene complexation ethers and 51.6g is dissolved in the toluene of 50ml, adds the adjacent benzene of 7.3g
The AIBN of dioctyl phthalate stannum, the ethylene glycol dimethacrylate of 15g and 1g, after stirring at normal temperature 40min, is heated in an oscillator
60 DEG C, ultrasonic vibration dissolving 1.5h obtains white precipitate, the support powder that particle diameter is 0.5 μm is ground to after sucking filtration, drying；
S4, the support powder of 15g is dissolved in the ethylene glycol of 70ml, is warming up to 70 DEG C, the graphene oxide of excessive addition is in three
In mouth flask, 0.4h is stood after stirring reaction 1.2h, carrier solution is filtered to obtain, the surface for being coated onto electrode forms oxidation stone
Black alkene single crystalline layer carrier.
The carrier supported catalyst prepared using the embodiment of the present invention 1, respectively in 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C of environment
Lower its monocell performance of measurement, as shown in figure 1, the electric current density highest under identical cell voltage, in the environment of 20 DEG C.
Embodiment two
The carrier of the electrode catalyst of a proton exchanging film fuel battery proposed by the present invention, the carrier is by Graphene and alkene
Propyl glycidyl ether, H2SnCl6After being reacted with 4,4- diphthalic anhydrides respectively, product is reacted, most
Carrier solution is obtained with graphite oxide alkene reaction afterwards.
Its preparation method, specifically includes following steps：
S1, by 30g Graphenes stirring and dissolving in 90ml deionized waters, be warming up to 88 DEG C, be slowly added to the concentration of 12ml successively
For the allyl glycidyl ether of the NaOH solution and 4ml of 2mol/L, stir while adding, after the completion of reaction, be cooled to room temperature,
Separated out with excess ethyl alcohol and precipitated, and be washed with deionized twice, remove unreacted allyl glycidyl ether, drying is obtained
Graphene complexation ether；
S2, by the H of 10g2SnCl6Be dissolved in the DMSO solvents of 45ml, oil bath is warming up to 78 DEG C, add 4.5ml to diformazan
Aminopyridine, after reaction 0.6h, adds 4, the 4- diphthalic anhydrides of 9ml, after reaction 1.2h, is cooled to room temperature, with foot
The ethyl acetate of amount separates out precipitation, and with washing with alcohol twice, removes unreacted impurity, and drying obtains phthalic acid stannum；
S3, the α-methacrylic acid of 8.4g Graphene complexation ethers and 49.5g is dissolved in the toluene of 48ml, adds the adjacent benzene of 6.6g
The AIBN of dioctyl phthalate stannum, the ethylene glycol dimethacrylate of 12g and 0.8g, after stirring at normal temperature 35min, is heated in an oscillator
To 58 DEG C, ultrasonic vibration dissolving 1h obtains white precipitate, the support powder that particle diameter is 5 μm is ground to after sucking filtration, drying；
S4, the support powder of 15g is dissolved in the ethylene glycol of 80ml, is warming up to 60 DEG C, the graphene oxide of excessive addition is in three
In mouth flask, 0.6h is stood after stirring reaction 1h, carrier solution is filtered to obtain, the surface for being coated onto electrode forms graphite oxide
Alkene single crystalline layer carrier.
The carrier supported catalyst prepared using the embodiment of the present invention 2, respectively in 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C of environment
Lower its monocell performance of measurement, as shown in Fig. 2 the electric current density highest under identical cell voltage, in the environment of 20 DEG C.
Embodiment three
The carrier of the electrode catalyst of a proton exchanging film fuel battery proposed by the present invention, the carrier is by Graphene and alkene
Propyl glycidyl ether, H2SnCl6After being reacted with 4,4- diphthalic anhydrides respectively, product is reacted, most
Carrier solution is obtained with graphite oxide alkene reaction afterwards.
Its preparation method, specifically includes following steps：
S1, by 30g Graphenes stirring and dissolving in 120ml deionized waters, be warming up to 80 DEG C, be slowly added to the concentration of 9ml successively
For the allyl glycidyl ether of the NaOH solution and 6ml of 2mol/L, stir while adding, after the completion of reaction, be cooled to room temperature,
Separated out with excess ethyl alcohol and precipitated, and be washed with deionized twice, remove unreacted allyl glycidyl ether, drying is obtained
Graphene complexation ether；
S2, by the H of 10g2SnCl6Be dissolved in the DMSO solvents of 50ml, oil bath is warming up to 85 DEG C, add 6ml to diformazan ammonia
Yl pyridines, after reaction 1h, add 4, the 4- diphthalic anhydrides of 12ml, after reaction 2h, are cooled to room temperature, with enough second
Acetoacetic ester separates out precipitation, and with washing with alcohol twice, removes unreacted impurity, and drying obtains phthalic acid stannum；
S3, the α-methacrylic acid of 8.4g Graphene complexation ethers and 52g is dissolved in the toluene of 52ml, adds the adjacent benzene two of 7.7g
The AIBN of formic acid stannum, the ethylene glycol dimethacrylate of 14g and 0.85g, after stirring at normal temperature 50min, is heated in an oscillator
To 65 DEG C, ultrasonic vibration dissolving 1.8h obtains white precipitate, the support powder that particle diameter is 10 μm is ground to after sucking filtration, drying；
S4, the support powder of 15g is dissolved in the ethylene glycol of 69ml, is warming up to 75 DEG C, the graphene oxide of excessive addition is in three
In mouth flask, 0.5h is stood after stirring reaction 1.5h, carrier solution is filtered to obtain, the surface for being coated onto electrode forms oxidation stone
Black alkene single crystalline layer carrier.
The carrier supported catalyst prepared using the embodiment of the present invention 3, respectively in 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C of environment
Lower its monocell performance of measurement, as shown in figure 3, the electric current density highest under identical cell voltage, in the environment of 20 DEG C.
Example IV
The carrier of the electrode catalyst of a proton exchanging film fuel battery proposed by the present invention, the carrier is by Graphene and alkene
Propyl glycidyl ether, H2SnCl6After being reacted with 4,4- diphthalic anhydrides respectively, product is reacted, most
Carrier solution is obtained with graphite oxide alkene reaction afterwards.
Its preparation method, specifically includes following steps：
S1, by 30g Graphenes stirring and dissolving in 125ml deionized waters, be warming up to 90 DEG C, be slowly added to the concentration of 15ml successively
For the allyl glycidyl ether of the NaOH solution and 7ml of 2mol/L, stir while adding, after the completion of reaction, be cooled to room temperature,
Separated out with excess ethyl alcohol and precipitated, and be washed with deionized twice, remove unreacted allyl glycidyl ether, drying is obtained
Graphene complexation ether；
S2, by the H of 10g2SnCl6Be dissolved in the DMSO solvents of 55ml, oil bath is warming up to 88 DEG C, add 5.5ml to diformazan
Aminopyridine, after reaction 0.9h, adds 4, the 4- diphthalic anhydrides of 11ml, after reaction 1.8h, is cooled to room temperature, with foot
The ethyl acetate of amount separates out precipitation, and with washing with alcohol twice, removes unreacted impurity, and drying obtains phthalic acid stannum；
S3, the α-methacrylic acid of 8.4g Graphene complexation ethers and 48.8g is dissolved in the toluene of 47ml, adds the adjacent benzene two of 7g
The AIBN of formic acid stannum, the ethylene glycol dimethacrylate of 13g and 0.9g, after stirring at normal temperature 30min, is heated in an oscillator
68 DEG C, ultrasonic vibration dissolving 2h obtains white precipitate, the support powder that particle diameter is 1 μm is ground to after sucking filtration, drying；
S4, the support powder of 15g is dissolved in the ethylene glycol of 82ml, is warming up to 65 DEG C, the graphene oxide of excessive addition is in three
In mouth flask, 0.6h is stood after stirring reaction 1.4h, carrier solution is filtered to obtain, the surface for being coated onto electrode forms oxidation stone
Black alkene single crystalline layer carrier.
The carrier supported catalyst prepared using the embodiment of the present invention 4, respectively in 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C of environment
Lower its monocell performance of measurement, as shown in figure 4, the electric current density highest under identical cell voltage, in the environment of 20 DEG C.
Embodiment five
The carrier of the electrode catalyst of a proton exchanging film fuel battery proposed by the present invention, the carrier is by Graphene and alkene
Propyl glycidyl ether, H2SnCl6After being reacted with 4,4- diphthalic anhydrides respectively, product is reacted, most
Carrier solution is obtained with graphite oxide alkene reaction afterwards.
Its preparation method, specifically includes following steps：
S1, by 30g Graphenes stirring and dissolving in 110ml deionized waters, be warming up to 85 DEG C, be slowly added to the concentration of 14ml successively
For the allyl glycidyl ether of the NaOH solution and 7.5ml of 2mol/L, stir while adding, after the completion of reaction, be cooled to room
Temperature, is separated out with excess ethyl alcohol and is precipitated, and is washed with deionized twice, removes unreacted allyl glycidyl ether, drying
Obtain Graphene complexation ether；
S2, by the H of 10g2SnCl6Be dissolved in the DMSO solvents of 48ml, oil bath is warming up to 76 DEG C, add 4ml to diformazan ammonia
Yl pyridines, after reaction 0.7h, add 4, the 4- diphthalic anhydrides of 10ml, after reaction 1.4h, are cooled to room temperature, with enough
Ethyl acetate separate out precipitation, and with washing with alcohol twice, remove unreacted impurity, drying obtains phthalic acid stannum；
S3, the α-methacrylic acid of 8.4g Graphene complexation ethers and 50.5g is dissolved in the toluene of 54ml, adds the adjacent benzene of 7.5g
The AIBN of dioctyl phthalate stannum, the ethylene glycol dimethacrylate of 12.5g and 0.95g, after stirring at normal temperature 45min, in an oscillator
62 DEG C are heated to, ultrasonic vibration dissolving 1.2h obtains white precipitate, the support powder that particle diameter is 8 μm is ground to after sucking filtration, drying；
S4, the support powder of 15g is dissolved in the ethylene glycol of 75ml, is warming up to 68 DEG C, the graphene oxide of excessive addition is in three
In mouth flask, 0.4h is stood after stirring reaction 1.1h, carrier solution is filtered to obtain, the surface for being coated onto electrode forms oxidation stone
Black alkene single crystalline layer carrier.
The carrier supported catalyst prepared using the embodiment of the present invention 5, respectively in 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C of environment
Lower its monocell performance of measurement, as shown in figure 5, the electric current density highest under identical cell voltage, in the environment of 20 DEG C.
The carrier that the embodiment of the present invention one～five is prepared loads same amount of Pt/C catalyst, measurement catalysis profit respectively
With rate, following result is drawn：
| Embodiment | One | Two | Three | Four | Five |
| Catalysis utilization rate | 52.0% | 48.6% | 51.8% | 53.1% | 52.6% |
In the case of load identical Pt/C catalyst, the catalysis utilization rate of existing carrier is 30% or so, has the above table can
Know, carrier proposed by the present invention can effectively improve the catalytic efficiency of catalyst, improve its catalysis utilization rate.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, should all be included within the scope of the present invention.
Claims (10)
1. the carrier of the electrode catalyst of a proton exchanging film fuel battery, it is characterised in that the carrier by Graphene and
Allyl glycidyl ether, H2SnCl6After being reacted with 4,4- diphthalic anhydrides respectively, product is reacted,
Carrier solution is obtained with graphite oxide alkene reaction finally.
2. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery, it is characterised in that including following
Step：
S1, Graphene and allyl glycidyl ether reaction are obtained into Graphene complexation ether；
S2, by H2SnCl6Phthalic acid stannum is obtained with the reaction of 4,4- diphthalic anhydrides；
S3, by Graphene complexation ether and phthalic acid stannum reaction be obtained support powder；
S4, support powder and graphite oxide alkene reaction are obtained into carrier solution.
3. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 2,
Characterized in that, step S1 is specially：In mass ratio 1:2.8～4.3 ratio, by Graphene stirring and dissolving in deionization
In water, 80～90 DEG C are warming up to, are slowly added to NaOH solution and allyl glycidyl ether successively, stir while adding, reacted
After the completion of, room temperature is cooled to, is separated out with excess ethyl alcohol and is precipitated, and be washed with deionized twice, remove unreacted pi-allyl
Glycidyl ether, drying obtain Graphene complexation ether.
4. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 3,
Characterized in that, the concentration of the NaOH solution is 2mol/L, and 0.3～0.5 times for Graphene amount of addition, the pi-allyl
0.12～0.25 times for Graphene amount of the addition of glycidyl ether.
5. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 2,
Characterized in that, step S2 is specially：In mass ratio 1:4.5～5.5 ratio, by H2SnCl6It is dissolved in DMSO solvents
In, oil bath is warming up to 76～88 DEG C, adds to dimethylamino naphthyridine, after 0.6～1h of reaction, adds 4,4-, bis- phthalic acids
Acid anhydride, after 1.2～2h of reaction, is cooled to room temperature, separates out precipitation with enough ethyl acetate, and with washing with alcohol twice, removes not
The impurity of reaction, drying, obtains phthalic acid stannum.
6. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 5,
Characterized in that, the addition to dimethylamino naphthyridine is H2SnCl60.4～0.6 times of amount, 4, the 4-, bis- adjacent benzene two
The addition of formic anhydride is H2SnCl60.9～1.2 times of amount.
7. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 2,
Characterized in that, step S3 is specially：In mass ratio 1:5.8～6.25：5.5～6.5 ratio, by Graphene complexation ether
It is dissolved in toluene with α-methacrylic acid, adds phthalic acid stannum, ethylene glycol dimethacrylate and AIBN, stirring at normal temperature
After 30～50min, 58～68 DEG C are heated in an oscillator, ultrasonic vibration dissolves 1～2h, obtains white precipitate, after sucking filtration, drying
It is ground to the support powder that particle diameter is 0.1～10 μm.
8. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 7,
Characterized in that, 0.78～0.92 times for Graphene complexation ether amount of the addition of the phthalic acid stannum, the ethylene glycol
1.35～1.82 times for Graphene complexation ether amount of the addition of dimethylacrylate.
9. the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 7, it is characterised in that
0.09～0.13 times for Graphene complexation ether amount of the addition of the AIBN.
10. the preparation method of the carrier of the electrode catalyst of a proton exchanging film fuel battery according to claim 2,
Characterized in that, step S4 in the preparation method is specially：In mass ratio 1～1.2:4.6～5.5 ratio, by carrier
Powder is dissolved in ethylene glycol, is warming up to 60～75 DEG C, the graphene oxide of excessive addition in there-necked flask, stirring reaction 1～
0.4～0.6h is stood after 1.5h, carrier solution is filtered to obtain, the surface for being coated onto electrode forms graphene oxide single crystalline layer load
Body.
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| CN102814176A (en) * | 2012-08-06 | 2012-12-12 | 太原理工大学 | Method for preparing platinum-tin graphene catalyst quickly |
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