CN104752736B - It is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as platinum based catalyst of carrier and preparation method thereof - Google Patents
It is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as platinum based catalyst of carrier and preparation method thereof Download PDFInfo
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- CN104752736B CN104752736B CN201510080275.5A CN201510080275A CN104752736B CN 104752736 B CN104752736 B CN 104752736B CN 201510080275 A CN201510080275 A CN 201510080275A CN 104752736 B CN104752736 B CN 104752736B
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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
- H01M4/92—Metals of platinum group
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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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 present invention relates to it is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as platinum based catalyst of carrier and preparation method thereof, be that a kind of use forms the loose three-dimensional netted structure run through as the catalyst of carrier loaded nano-platinum particle to improve the method for catalyst activity and durability and its application for Proton Exchange Membrane Fuel Cells by porous carbon nanofiber.The platinum based catalyst using porous carbon nanofiber as carrier, the porous carbon nanofiber as carrier form the loose three-dimensional netted structure run through, metal platinum are supported with porous carbon nanofiber；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%；The durability using porous carbon nanofiber as the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations.
Description
Technical field
The invention belongs to catalyst technical field, be related to it is a kind of with high catalytic activity and high-durability with porous carbon nanometer
Fiber is platinum based catalyst of carrier and preparation method thereof and its application, and more particularly to one kind improves Proton Exchange Membrane Fuel Cells
It is a kind of use by porous carbon nanometer specifically with the catalytic activity of platinum carbon catalyst and the method and its application of durability
Fiber forms the loose three-dimensional netted structure run through and urged as the catalyst of carrier loaded nano-platinum particle with improving catalyst
Change the method for activity and durability and its application for Proton Exchange Membrane Fuel Cells.
Background technology
Proton Exchange Membrane Fuel Cells due to its with the clean pollution-free, fuel cell such as energy conversion rate is high be total to
Outside with feature, it is also equipped with fast toggle speed, the leakage of electroless matter and corrodes low advantage, become in world wide and study
One of focus.Therefore the today's society of environmental pollution and energy crisis is being paid high attention to, Proton Exchange Membrane Fuel Cells has very much
Wish to use as follow-on novel battery, turn into the main force in energy field.
The core component membrane electrode assembly (MEA) of Proton Exchange Membrane Fuel Cells, is electrochemical reaction place, membrane electrode
Performance has close relationship with its structure composition, therefore improvement film electrode structure composition has important meaning to improving battery performance
Justice.Catalyst wherein as reaction electrode, its expensive price seriously govern combustion with relatively low activity, efficiency and life-span
Expect performance and the development of battery.Research direction mainly has two at present, reduces the dosage of the noble metals such as platinum, palladium, or with to expensive
Metal alloy is substituted completely, and the cost of catalyst and fuel cell, but the activity of the catalyst of the method reduction are reduced with this, is cut
The performance of fuel cell is subtracted.Another scheme is mainly by changing the composition and pattern of catalyst carrier, but due to carrier
Prepare, the load process of catalyst is numerous and diverse, pollution be present, and catalyst performance is unstable and fail to be commercialized.
The content of the invention
The technical problems to be solved by the invention be to provide it is a kind of with high catalytic activity and high-durability with porous carbon
Nanofiber is platinum based catalyst of carrier and preparation method thereof and its application, is especially to provide a kind of improvement PEM combustion
Expect the catalytic activity of battery platinum carbon catalyst and the method and its application of durability, be a kind of use by porous specifically
Carbon nano-fiber forms the loose three-dimensional netted structure run through as carrier loaded platinum carbon catalyst to improve platinum carbon catalyst
The method of catalytic activity and durability and its application for Proton Exchange Membrane Fuel Cells.
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent and preparation method thereof and its application, are blended with porous carbon nanofiber and commercialization platinum carbon catalyst, with porous carbon nanometer
Fiber, as compound carbon carrier, improves platinum carbon catalyst catalytic activity and durability with carbon black.Utilize porous carbon nanofiber table
The active site that planar defect provides causes platinum grain to be migrated by carbon blacksurface and is fixed on porous carbon nanofiber surface.Porous carbon is received
The pore structure of rice fibre-enrich, and suitable draw ratio, not only increase catalyst activity, are more formed in electrode structure
Loose layer structure, improves the life-span of catalyst, and reduces the mass transfer polarization of membrane electrode, so as to further increasing
The power generation performance of fuel cell.
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent, the porous carbon nanofiber as carrier forms the loose three-dimensional netted structure run through, on porous carbon nanofiber
It is supported with metal platinum；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Spike potential is played than platinum charcoal
Catalyst shifts to an earlier date 100 millivolts, and platinum utilization reaches 80%, far above the 45% of prior art；It is described with porous carbon Nanowire
Tie up the durability of the platinum based catalyst for carrier：ECSA conservation rates reach 50% after 1000 circulations, far above prior art
5%.The hole on porous carbon nanofiber surface and defect provide more active sites, it is possible to increase the catalysis of Pt nanoparticle is lived
Property；Meanwhile the hole on porous carbon nanofiber surface and defect can anchor platinum grain, improve the durability of catalyst.
As preferable technical scheme：
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability as described above
Catalyst, carbon black is also supported with the porous carbon nanofiber, and metal platinum is loaded with carbon black.Porous carbon nanofiber table
The hole in face and defect are advantageous to the scattered of Pt nanoparticle, can be obviously improved the dispersiveness of Pt nanoparticle, while porous carbon
Nanofiber can also disperse to carbon black pellet, further increase the dispersiveness of platinum.The improvement of dispersiveness causes more platinum
Nano particle is exposed, and can effectively improve platinum utilization.
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability as described above
Catalyst, the average fibre diameter of the porous carbon nanofiber is 100~1000 nanometers, and aperture is 5~100 nanometers, fiber
Draw ratio is 5~30.Because porous carbon nanofiber has certain draw ratio, it is possible to prevente effectively from catalyst is tightly packed,
When building electrode, porous carbon nanofiber forms a loose three-dimensional netted structure run through in the electrodes, is advantageous to subtract
Small resistance to mass tranfer, while be advantageous to the exclusion of reaction product, avoid catalyst water logging from inactivating.
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability as described above
Catalyst, using porous carbon nanofiber as in the platinum based catalyst of carrier, the content of the platinum is 10wt%~40wt%.
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability as described above
Catalyst, using porous carbon nanofiber as in the platinum based catalyst of carrier, content≤50wt% of the carbon black.
Present invention also offers it is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as carrier
The preparation method of platinum based catalyst, by porous carbon nanofiber and platinum carbon catalyst common distribution in dispersant, it is ultrasonically treated
After dry, that is, obtain the platinum based catalyst using porous carbon nanofiber as carrier using porous carbon nanofiber as carrier.
Preparation method as described above, the dispersant are isopropanol or methanol；Platinum content is in the platinum carbon catalyst
15wt%~60wt%, remaining is carbon black；20~40nm of particle diameter of the platinum carbon catalyst；The supersound process refers to 50 hertz
Frequency ultrasound hereby is handled 0.5~4 hour；The drying refers to dry 6~12 hours at a temperature of 40~120 DEG C.
Invention further provides it is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as carrier
The preparation method of platinum based catalyst, it is to be reduced in the form of nano particle platinum by the method for electronation by the presoma of platinum
It is carried on carbon carrier porous carbon nanofiber.Such as according to document【Songli Wei,Dingcai Wu,Xuelong Shang,
Ruowen Fu,Studies on the Structure and Electrochemical Performance of Pt/
Carbon Aerogel Catalyst for Direct Methanol Fuel Cells,Energy&Fuels,23(2009)
908–911】Described method.Platinum is reduced and is carried on carbon aerogels from chloroplatinic acid by spent glycol liquid phase reduction.
Invention further provides a kind of using porous carbon nanofiber as the monocell obtained by the platinum based catalyst of carrier, by
Membrane electrode assembly forms between being placed in anode and cathode flow-field plate, and the membrane electrode assembly is by the platinum using porous carbon nanofiber as carrier
Base catalyst is sprayed at PEM cathode side and anode-side obtains through hot pressing；Membrane electrode assembly resistance value is 200-500 Europe
Nurse.
Monocell as described above, the amount of the spraying is 0.2-0.8mg-Pt/cm2；The temperature of the hot pressing is 50-
150℃。
The porous carbon nanofiber of the present invention provides further disperseing for platinum, and applied to pem fuel electricity
Chi Shineng builds loose catalyst layer mechanism, advantageously reduces resistance to mass tranfer.
Beneficial effect
1. being used as compound carbon carrier by adding porous carbon nanofiber, catalyst activity, and oxygen are effectively raised
Reduction reaction rate, so as to significantly improve catalyst use efficiency；
2. being used as compound carbon carrier by adding porous carbon nanofiber, urging with three-dimensional UNICOM's structure can be effectively built
Agent layer, the polarization of membrane electrode mass transfer is reduced, and catalyst granules is further disperseed, improve the power generation performance of fuel cell；
3. in the present invention, it is not necessary to extra load process etc. is carried out to porous carbon nanofiber, therefore its technique is simple,
It is easy to operate, it is easy to be commercialized；
4. porous carbon nanofiber of the present invention, cost is cheap, prepares simply, pollution-free.
5. for the present invention when building electrode, porous carbon nanofiber forms the loose three-dimensional netted knot run through in the electrodes
Structure, be advantageous to the exclusion of reaction product, avoid catalyst water logging from inactivating.
Brief description of the drawings
Fig. 1 is porous carbon nanofiber surface topography
Fig. 2 is porous carbon nanofiber cross-section morphology
Fig. 3 is by the platinum based catalyst platinum made from the chemical reduction method of the present invention using porous carbon nanofiber as carrier
Content is 10%, Pt/PCNFs-10 surface topographies
Fig. 4 is by the platinum based catalyst platinum made from the chemical reduction method of the present invention using porous carbon nanofiber as carrier
Content is 40%, Pt/PCNFs-40 transmission electron microscope pictures
Fig. 5 is by the platinum based catalyst platinum made from the chemical reduction method of the present invention using porous carbon nanofiber as carrier
Content is 20%, Pt/PCNFs-20 transmission electron microscope pictures
Fig. 6 is by the platinum based catalyst platinum made from the dispersion mixing method of the present invention using porous carbon nanofiber as carrier
Content is 20%, Pt/PCNFs-20 transmission electron microscope pictures
Platinum based catalyst electrode surface patterns of the Fig. 7 using porous carbon nanofiber as carrier
Platinum based catalyst electrode cross-section morphologies of the Fig. 8 using porous carbon nanofiber as carrier
Platinum based catalyst electrode cross-section morphologies of the Fig. 9 using porous carbon nanofiber as carrier
Figure 10 different catalysts linear scan curves, wherein Pt/PCNFs-20 are the dispersion mixing legal system by the present invention
The platinum based catalyst platinum content using porous carbon nanofiber as carrier obtained is 20%；JM-20 is Johnson Matthey
Corporation HiSPEC3000 platinum carbon catalysts；JM-40 is Johnson Matthey Corporation
HiSPEC4000 platinum carbon catalysts.
Figure 11 different catalysts ECSA durability, wherein Pt/PCNFs-20 are to be made by the chemical reduction method of the present invention
The platinum based catalyst platinum content using porous carbon nanofiber as carrier be 20%；Pt/Vulcan-20 is the charcoal catalysis of self-control platinum
Agent, platinum content 20%；JM-20 is Johnson Matthey Corporation HiSPEC3000 platinum carbon catalysts.
Figure 12 monocell polarization curves, wherein Pt/PCNFs-20 be by the present invention dispersion mixing method made from more
Hole carbon nano-fiber is that the platinum based catalyst platinum content of carrier is 20%；JM-20 is Johnson Matthey Corporation
HiSPEC3000 platinum carbon catalysts；JM-40 is Johnson Matthey Corporation HiSPEC4000 platinum carbon catalysts.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent, be illustrated in figure 7 the platinum based catalyst electrode surface pattern using porous carbon nanofiber as carrier, be illustrated in figure 8 with
Porous carbon nanofiber is the platinum based catalyst electrode cross-section morphology of carrier, is illustrated in figure 9 using porous carbon nanofiber as load
The platinum based catalyst electrode cross-section morphology of body, the wherein content of platinum are 10wt%, and the porous carbon nanofiber as carrier is formed
The loose three-dimensional netted structure run through, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber section
Pattern, the average fibre diameter of porous carbon nanofiber is 100 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 5,
Metal platinum is supported with porous carbon nanofiber；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：
Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above the 45% of prior art；Should be with
Porous carbon nanofiber is the durability of the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations, remote high
In the 5% of prior art.
Embodiment 2
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent, be illustrated in figure 7 the platinum based catalyst electrode surface pattern using porous carbon nanofiber as carrier, be illustrated in figure 8 with
Porous carbon nanofiber is the platinum based catalyst electrode cross-section morphology of carrier, is illustrated in figure 9 using porous carbon nanofiber as load
The platinum based catalyst electrode cross-section morphology of body, the wherein content of platinum are 40wt%, and the porous carbon nanofiber as carrier is formed
The loose three-dimensional netted structure run through, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber section
Pattern, the average fibre diameter of porous carbon nanofiber is 1000 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 30,
Metal platinum is supported with porous carbon nanofiber；This using porous carbon nanofiber as the platinum based catalyst of carrier catalysis live
Property：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above the 45% of prior art；Should
Durability using porous carbon nanofiber as the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations, far
Higher than the 5% of prior art.
Embodiment 3
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent, be illustrated in figure 7 the platinum based catalyst electrode surface pattern using porous carbon nanofiber as carrier, be illustrated in figure 8 with
Porous carbon nanofiber is the platinum based catalyst electrode cross-section morphology of carrier, is illustrated in figure 9 using porous carbon nanofiber as load
The platinum based catalyst electrode cross-section morphology of body, the wherein content of platinum are 20wt%, and the porous carbon nanofiber as carrier is formed
The loose three-dimensional netted structure run through, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber section
Pattern, the average fibre diameter of porous carbon nanofiber is 800 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 10,
Metal platinum is supported with porous carbon nanofiber；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：
Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above the 45% of prior art；Should be with
Porous carbon nanofiber is the durability of the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations, remote high
In the 5% of prior art.
Embodiment 4
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent, be illustrated in figure 7 the platinum based catalyst electrode surface pattern using porous carbon nanofiber as carrier, be illustrated in figure 8 with
Porous carbon nanofiber is the platinum based catalyst electrode cross-section morphology of carrier, is illustrated in figure 9 using porous carbon nanofiber as load
The platinum based catalyst electrode cross-section morphology of body, the porous carbon nanofiber as carrier form the loose three-dimensional netted knot run through
Structure, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber cross-section morphology, the fibre of porous carbon nanofiber
It is 100 nanometers to tie up average diameter, and aperture is 5~100 nanometers, Fiber Aspect Ratio 30, is supported with porous carbon nanofiber
Metal platinum, carbon black is also supported with, and metal platinum is loaded with carbon black, in the platinum based catalyst, the content 50wt% of carbon black, platinum
Content be 40wt%；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Spike potential is played than platinum charcoal
Catalyst shifts to an earlier date 100 millivolts, and platinum utilization reaches 80%, far above the 45% of prior art；Should be with porous carbon nanofiber
For the durability of the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations, far above prior art
5%.
Embodiment 5
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent, be illustrated in figure 7 the platinum based catalyst electrode surface pattern using porous carbon nanofiber as carrier, be illustrated in figure 8 with
Porous carbon nanofiber is the platinum based catalyst electrode cross-section morphology of carrier, is illustrated in figure 9 using porous carbon nanofiber as load
The platinum based catalyst electrode cross-section morphology of body, the porous carbon nanofiber as carrier form the loose three-dimensional netted knot run through
Structure, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber cross-section morphology, the fibre of porous carbon nanofiber
It is 1000 nanometers to tie up average diameter, and aperture is 5~100 nanometers, Fiber Aspect Ratio 5, is supported with porous carbon nanofiber
Metal platinum, carbon black is also supported with, and metal platinum is loaded with carbon black, in the platinum based catalyst, the content 30wt% of carbon black, platinum
Content be 10wt%；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Spike potential is played than platinum charcoal
Catalyst shifts to an earlier date 100 millivolts, and platinum utilization reaches 80%, far above the 45% of prior art；Should be with porous carbon nanofiber
For the durability of the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations, far above prior art
5%.
Embodiment 6
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
Agent, be illustrated in figure 7 the platinum based catalyst electrode surface pattern using porous carbon nanofiber as carrier, be illustrated in figure 8 with
Porous carbon nanofiber is the platinum based catalyst electrode cross-section morphology of carrier, is illustrated in figure 9 using porous carbon nanofiber as load
The platinum based catalyst electrode cross-section morphology of body, the porous carbon nanofiber as carrier form the loose three-dimensional netted knot run through
Structure, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber cross-section morphology, the fibre of porous carbon nanofiber
It is 800 nanometers to tie up average diameter, and aperture is 5~100 nanometers, Fiber Aspect Ratio 10, is supported with porous carbon nanofiber
Metal platinum, carbon black is also supported with, and metal platinum is loaded with carbon black, in the platinum based catalyst, the content 40wt% of carbon black, platinum
Content be 20wt%；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Spike potential is played than platinum charcoal
Catalyst shifts to an earlier date 100 millivolts, and platinum utilization reaches 80%, far above the 45% of prior art；Should be with porous carbon nanofiber
For the durability of the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations, far above prior art
5%.
Embodiment 7
The monocell of the present invention, using porous carbon nanofiber as obtained by the platinum based catalyst of carrier, by membrane electrode assembly
It is placed between anode and cathode flow-field plate and forms, the porous carbon nanofiber is the platinum based catalyst of carrier, is illustrated in figure 7 with porous carbon
Nanofiber is the platinum based catalyst electrode surface pattern of carrier, is illustrated in figure 8 the platinum using porous carbon nanofiber as carrier
Base catalyst electrode cross-section morphology, it is illustrated in figure 9 the platinum based catalyst electrode section shape using porous carbon nanofiber as carrier
The content of looks, wherein platinum is 10wt%, and the porous carbon nanofiber as carrier forms the loose three-dimensional netted structure run through,
Fig. 1 is porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber cross-section morphology, the fiber of porous carbon nanofiber
Average diameter is 100 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 5, metal is supported with porous carbon nanofiber
Platinum；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Play spike potential and shift to an earlier date 100 than platinum carbon catalyst
Millivolt, platinum utilization reaches 80%, far above the 45% of prior art；The platinum base using porous carbon nanofiber as carrier is urged
The durability of agent：ECSA conservation rates reach 50% after 1000 circulations, and far above the 5% of prior art, membrane electrode assembly is
PEM cathode side is sprayed at by the platinum based catalyst using porous carbon nanofiber as carrier and anode-side obtains through hot pressing,
The amount of spraying is 0.2mg-Pt/cm2；The temperature of hot pressing is 50 DEG C；Membrane electrode assembly resistance value is 200 ohm.
Embodiment 8
The monocell of the present invention, using porous carbon nanofiber as obtained by the platinum based catalyst of carrier, by membrane electrode assembly
It is placed between anode and cathode flow-field plate and forms, the porous carbon nanofiber is the platinum based catalyst of carrier, is illustrated in figure 7 with porous carbon
Nanofiber is the platinum based catalyst electrode surface pattern of carrier, is illustrated in figure 8 the platinum using porous carbon nanofiber as carrier
Base catalyst electrode cross-section morphology, it is illustrated in figure 9 the platinum based catalyst electrode section shape using porous carbon nanofiber as carrier
The content of looks, wherein platinum is 40wt%, and the porous carbon nanofiber as carrier forms the loose three-dimensional netted structure run through,
Fig. 1 is porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber cross-section morphology, the fiber of porous carbon nanofiber
Average diameter is 1000 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 30, gold is supported with porous carbon nanofiber
Belong to platinum；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Spike potential is played than platinum carbon catalyst to shift to an earlier date
100 millivolts, platinum utilization reaches 80%, far above the 45% of prior art；The platinum using porous carbon nanofiber as carrier
The durability of base catalyst：ECSA conservation rates reach 50% after 1000 circulations, far above the 5% of prior art, membrane electrode assembly
Part is to be sprayed at PEM cathode side and anode-side through hot pressing by the platinum based catalyst using porous carbon nanofiber as carrier
It is made, the amount of spraying is 0.8mg-Pt/cm2；The temperature of hot pressing is 150 DEG C；Membrane electrode assembly resistance value is 500 ohm.
Embodiment 9
The monocell of the present invention, using how empty carbon nano-fiber as obtained by the platinum based catalyst of carrier, by membrane electrode assembly
It is placed between anode and cathode flow-field plate and forms, platinum based catalyst that should be using porous carbon nanofiber as carrier is illustrated in figure 7 with porous
Carbon nano-fiber is the platinum based catalyst electrode surface pattern of carrier, is illustrated in figure 8 using porous carbon nanofiber as carrier
Platinum based catalyst electrode cross-section morphology, it is illustrated in figure 9 the platinum based catalyst electrode section using porous carbon nanofiber as carrier
Pattern, the porous carbon nanofiber as carrier form the loose three-dimensional netted structure run through, and Fig. 1 is porous carbon nanofiber
Surface topography, Fig. 2 are porous carbon nanofiber cross-section morphology, and the average fibre diameter of porous carbon nanofiber is 1000 nanometers,
Aperture is 5~100 nanometers, Fiber Aspect Ratio 30, metal platinum is supported with porous carbon nanofiber, is also supported with carbon black,
And metal platinum is loaded with carbon black, in the platinum based catalyst, the content of carbon black is 50wt%, and the content of platinum is 10wt%；Should be with
Porous carbon nanofiber is the catalytic activity of the platinum based catalyst of carrier：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum
Utilization rate reach 80%, far above the 45% of prior art；This is using porous carbon nanofiber as the platinum based catalyst of carrier
Durability：ECSA conservation rates reach 50% after 1000 circulations, far above the 5% of prior art；The membrane electrode assembly be by with
Porous carbon nanofiber is sprayed at PEM cathode side for the platinum based catalyst of carrier and anode-side obtains through hot pressing, spraying
Amount be 0.2mg-Pt/cm2；The temperature of the hot pressing is 50 DEG C；Membrane electrode assembly resistance value is 200 ohm.
Embodiment 10
The monocell of the present invention, using how empty carbon nano-fiber as obtained by the platinum based catalyst of carrier, by membrane electrode assembly
It is placed between anode and cathode flow-field plate and forms, platinum based catalyst that should be using how empty carbon nano-fiber as carrier is illustrated in figure 7 with porous
Carbon nano-fiber is the platinum based catalyst electrode surface pattern of carrier, is illustrated in figure 8 using porous carbon nanofiber as carrier
Platinum based catalyst electrode cross-section morphology, it is illustrated in figure 9 the platinum based catalyst electrode section using porous carbon nanofiber as carrier
Pattern, the porous carbon nanofiber as carrier form the loose three-dimensional netted structure run through, and Fig. 1 is porous carbon nanofiber
Surface topography, Fig. 2 are porous carbon nanofiber cross-section morphology, and the average fibre diameter of porous carbon nanofiber is 800 nanometers, hole
Footpath is 5~100 nanometers, Fiber Aspect Ratio 8, metal platinum is supported with porous carbon nanofiber, is also supported with carbon black, and charcoal
Metal platinum is loaded with black, in the platinum based catalyst, the content 30wt% of carbon black, the content of platinum is 40wt%；Should be with porous carbon
Nanofiber is the catalytic activity of the platinum based catalyst of carrier：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, the utilization of platinum
Rate reaches 80%, far above the 45% of prior art；The durability using porous carbon nanofiber as the platinum based catalyst of carrier：
ECSA conservation rates reach 50% after 1000 circulations, far above the 5% of prior art；The membrane electrode assembly is by being received with porous carbon
Rice fiber is sprayed at PEM cathode side for the platinum based catalyst of carrier and anode-side obtains through hot pressing, and the amount of painting is
0.6mg-Pt/cm2；The temperature of hot pressing is 100 DEG C；Membrane electrode assembly resistance value is 300 ohm.
Embodiment 11
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
The preparation method of agent, it is 15wt% by porous carbon nanofiber and platinum content, remaining divides jointly for the platinum carbon catalyst of carbon black
It is dispersed in isopropyl alcohol dispersant, wherein 20~40nm of particle diameter of platinum carbon catalyst, then handles 0.5 with 50 hertz of frequency ultrasound
Dried 6 hours at a temperature of 40 DEG C after hour, that is, obtain the platinum based catalyst using porous carbon nanofiber as carrier, should be with porous carbon
Nanofiber is the platinum based catalyst of carrier, is illustrated in figure 7 the platinum based catalyst electrode using porous carbon nanofiber as carrier
Surface topography, the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier is illustrated in figure 8, as shown in Figure 9
For the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier, the porous carbon nanofiber as carrier is formed
The loose three-dimensional netted structure run through, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber section
Pattern, the average fibre diameter of porous carbon nanofiber is 100 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 5,
Metal platinum is supported with porous carbon nanofiber, is also supported with carbon black, and metal platinum is loaded with carbon black, in the platinum based catalyst
In, the content 50wt% of carbon black, the content of platinum is 10wt%；The urging using porous carbon nanofiber as the platinum based catalyst of carrier
Change activity：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above prior art
45%；The durability using porous carbon nanofiber as the platinum based catalyst of carrier：ECSA conservation rates reach after 1000 circulations
50%, far above the 5% of prior art.
Embodiment 12
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
The preparation method of agent, it is 60wt% by porous carbon nanofiber and platinum content, remaining divides jointly for the platinum carbon catalyst of carbon black
It is dispersed in dispersant methanol, wherein 20~40nm of particle diameter of platinum carbon catalyst, is then handled 4 hours with 50 hertz of frequency ultrasound
Dried 12 hours at a temperature of 120 DEG C afterwards, that is, obtain the platinum based catalyst using porous carbon nanofiber as carrier, should received with porous carbon
Rice fiber is the platinum based catalyst of carrier, is illustrated in figure 7 the platinum based catalyst electrode table using porous carbon nanofiber as carrier
Face pattern, the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier is illustrated in figure 8, is illustrated in figure 9
Platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier, the porous carbon nanofiber as carrier, which is formed, to be dredged
The three-dimensional netted structure run through of pine, Fig. 1 is porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber section shape
Looks, the average fibre diameter of porous carbon nanofiber is 1000 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 30,
Metal platinum is supported with porous carbon nanofiber, is also supported with carbon black, and metal platinum is loaded with carbon black, in the platinum based catalyst
In, the content 30wt% of carbon black, the content of platinum is 40wt%；The urging using porous carbon nanofiber as the platinum based catalyst of carrier
Change activity：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above prior art
45%；The durability using porous carbon nanofiber as the platinum based catalyst of carrier：ECSA conservation rates reach after 1000 circulations
50%, far above the 5% of prior art.
Embodiment 13
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
The preparation method of agent, it is 20wt% by porous carbon nanofiber and platinum content, remaining divides jointly for the platinum carbon catalyst of carbon black
It is dispersed in dispersant methanol, wherein the particle diameter of platinum carbon catalyst is 20~40nm, then small with 50 hertz of frequency ultrasound processing 2
When after dried 10 hours at a temperature of 80 DEG C, that is, obtain the platinum based catalyst using porous carbon nanofiber as carrier, should with porous carbon
Nanofiber is the platinum based catalyst of carrier, is illustrated in figure 7 the platinum based catalyst electrode using porous carbon nanofiber as carrier
Surface topography, the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier is illustrated in figure 8, as shown in Figure 9
For the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier, the porous carbon nanofiber as carrier is formed
The loose three-dimensional netted structure run through, Fig. 1 are porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber section
Pattern, the average fibre diameter of porous carbon nanofiber is 800 nanometers, and aperture is 5~100 nanometers, Fiber Aspect Ratio 6,
Metal platinum is supported with porous carbon nanofiber；Carbon black is also supported with, and metal platinum is loaded with carbon black, in the platinum based catalyst
In, the content 20wt% of carbon black, the content of platinum is 20wt%；The urging using porous carbon nanofiber as the platinum based catalyst of carrier
Change activity：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above prior art
45%；The durability using porous carbon nanofiber as the platinum based catalyst of carrier：ECSA conservation rates reach after 1000 circulations
50%, far above the 5% of prior art.It is as shown in Figure 10 different catalysts linear scan curve, wherein Pt/PCNFs-20 is
The obtained platinum based catalyst platinum content using porous carbon nanofiber as carrier is 20%；JM-20 is Johnson Matthey
Corporation HiSPEC3000 platinum carbon catalysts；JM-40 is Johnson Matthey Corporation
HiSPEC4000 platinum carbon catalysts.It is monocell polarization curve as shown in figure 12, wherein Pt/PCNFs-20 is by the present invention's
The obtained platinum based catalyst platinum content using porous carbon nanofiber as carrier of dispersion mixing method is 20%；JM-20 is Johnson
Matthey Corporation HiSPEC3000 platinum carbon catalysts；JM-40 is Johnson Matthey Corporation
HiSPEC4000 platinum carbon catalysts.
Embodiment 14
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
The preparation method of agent, be by platinum presoma by the method for electronation by platinum in the form of nano particle it is reducing loaded in
On carbon carrier porous carbon nanofiber, the porous carbon fiber for weighing 80mg first is placed in three-necked flask, adds 50ml second two
Alcohol ultrasonic disperse 1h, which is formed, divides equally scattered suspension, is then slowly added dropwise and adds a certain amount of chloroplatinic acid aqueous solution (so that platinum
The platinum carrying capacity of Pd/carbon catalyst is 15wt%), continue ultrasonic 1h, stir 2h, solution is warming up to 130 DEG C, N2Atmosphere protection flows back
3h, be cooled to room temperature, centrifuge out product, and with substantial amounts of washing several times, by product be placed in vacuum drying oven 80 DEG C it is true
Sky dries 12h, and producing the content using porous carbon nanofiber as carrier platinum with high catalytic activity and high-durability is
10wt% platinum based catalyst, it is illustrated in figure 3 the obtained platinum based catalyst platinum content using porous carbon nanofiber as carrier
For 10%, Pt/PCNFs-10 surface topographies, the platinum based catalyst electrode using porous carbon nanofiber as carrier is illustrated in figure 7
Surface topography, the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier is illustrated in figure 8, as shown in Figure 9
For the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier, the platinum based catalyst, as the porous of carrier
Carbon nano-fiber forms the loose three-dimensional netted structure run through, and Fig. 1 is porous carbon nanofiber surface topography, and Fig. 2 is porous
Carbon nano-fiber cross-section morphology, the average fibre diameter of porous carbon nanofiber is 100 nanometers, and aperture is 5~100 nanometers, fine
It is 5 to tie up draw ratio, and metal platinum is supported with porous carbon nanofiber；This using porous carbon nanofiber as carrier platinum base be catalyzed
The catalytic activity of agent：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above existing skill
The 45% of art；The durability using porous carbon nanofiber as the platinum based catalyst of carrier：ECSA conservation rates after 1000 circulations
Reach 50%, far above the 5% of prior art.
Embodiment 15
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
The preparation method of agent, be by platinum presoma by the method for electronation by platinum in the form of nano particle it is reducing loaded in
On carbon carrier porous carbon nanofiber, the porous carbon fiber for weighing 60mg first is placed in three-necked flask, adds 60ml boron hydrogen
Change sodium ultrasonic disperse 1h and form the suspension divided equally and disperseed, a certain amount of platinic sodium chloride aqueous solution of addition, which is then slowly added dropwise, (to be made
The platinum carrying capacity for obtaining platinum carbon catalyst is 20wt%), continue ultrasonic 2h, stir 2h, solution is warming up to 130 DEG C, N2Atmosphere protection
Flow back 3h, is cooled to room temperature, centrifuges out product, and with substantial amounts of washing several times, product is placed in 80 in vacuum drying oven
DEG C vacuum drying 12h, producing the content using porous carbon nanofiber as carrier platinum with high catalytic activity and high-durability is
20wt% platinum based catalyst, it is illustrated in figure 5 the obtained platinum based catalyst platinum content using porous carbon nanofiber as carrier
For 20%, Pt/PCNFs-20 transmission electron microscope pictures, the platinum based catalyst, it is illustrated in figure 7 using porous carbon nanofiber as carrier
Platinum based catalyst electrode surface pattern, it is illustrated in figure 8 the platinum based catalyst electrode section using porous carbon nanofiber as carrier
Pattern, the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier is illustrated in figure 9, as the porous of carrier
Carbon nano-fiber forms the loose three-dimensional netted structure run through, and Fig. 1 is porous carbon nanofiber surface topography, and Fig. 2 is porous
Carbon nano-fiber cross-section morphology, the average fibre diameter of porous carbon nanofiber is 1000 nanometers, and aperture is 5~100 nanometers, fine
It is 30 to tie up draw ratio, and metal platinum is supported with porous carbon nanofiber；The platinum base using porous carbon nanofiber as carrier is urged
The catalytic activity of agent：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%, far above existing
The 45% of technology；The durability using porous carbon nanofiber as the platinum based catalyst of carrier：ECSA is kept after 1000 circulations
Rate reaches 50%, far above the 5% of prior art.It is as shown in figure 11 different catalysts ECSA durability, wherein Pt/PCNFs-
The 20 platinum based catalyst platinum content using porous carbon nanofiber as carrier for made from is 20%；Pt/Vulcan-20 is self-control platinum
Pd/carbon catalyst, platinum content 20%；JM-20 is catalyzed for Johnson Matthey Corporation HiSPEC3000 platinum charcoal
Agent.
Embodiment 16
A kind of platinum base using porous carbon nanofiber as carrier with high catalytic activity and high-durability of the present invention is urged
The preparation method of agent, be by platinum presoma by the method for electronation by platinum in the form of nano particle it is reducing loaded in
On carbon carrier porous carbon nanofiber, the porous carbon fiber for weighing 30mg first is placed in three-necked flask, adds 80ml formic acid
Ultrasonic disperse 1h, which is formed, divides equally scattered suspension, is then slowly added dropwise and adds a certain amount of acetic acid platinum aqueous solution (so that platinum carbon
The platinum carrying capacity of catalyst is 60wt%), continue ultrasonic 2h, stir 2h, solution is warming up to 130 DEG C, N2Atmosphere protection backflow 3h,
Room temperature is cooled to, centrifuges out product, and with substantial amounts of washing several times, product is placed in 80 DEG C of vacuum in vacuum drying oven and done
Dry 12h, produce with high catalytic activity and high-durability using the content that porous carbon nanofiber is carrier platinum as 40wt%'s
Platinum based catalyst, it is 40% to be illustrated in figure 4 the obtained platinum based catalyst platinum content using porous carbon nanofiber as carrier,
Pt/PCNFs-40 transmission electron microscope pictures, there should be the platinum using porous carbon nanofiber as carrier of high catalytic activity and high-durability
Base catalyst, the platinum based catalyst electrode surface pattern using porous carbon nanofiber as carrier is illustrated in figure 7, as shown in Figure 8
For the platinum based catalyst electrode cross-section morphology using porous carbon nanofiber as carrier, it is illustrated in figure 9 with porous carbon nanofiber
For the platinum based catalyst electrode cross-section morphology of carrier, the porous carbon nanofiber as carrier forms loose three-dimensional netted run through
Structure, Fig. 1 is porous carbon nanofiber surface topography, and Fig. 2 is porous carbon nanofiber cross-section morphology, porous carbon nanofiber
Average fibre diameter be 800 nanometers, aperture be 5~100 nanometers, Fiber Aspect Ratio 8, supported on porous carbon nanofiber
There is metal platinum；The catalytic activity using porous carbon nanofiber as the platinum based catalyst of carrier：Play spike potential and compare platinum carbon catalyst
100 millivolts in advance, platinum utilization reaches 80%, far above the 45% of prior art；Should be using porous carbon nanofiber as carrier
Platinum based catalyst durability：1000 times circulation after ECSA conservation rates reach 50%, far above the 5% of prior art, with
Porous carbon nanofiber is in the platinum based catalyst of carrier, the content of platinum is 40wt%.
Claims (8)
1. a kind of platinum based catalyst using porous carbon nanofiber as carrier with high catalytic activity and high-durability, its feature
It is：The platinum based catalyst using porous carbon nanofiber as carrier, the interlaced structure of porous carbon nanofiber as carrier
Into the loose three-dimensional netted structure run through, the draw ratio of porous carbon nanofiber is 5~30, is carried on a shoulder pole on porous carbon nanofiber
Metal platinum and carbon black are loaded with, and metal platinum is loaded with carbon black；The platinum based catalyst using porous carbon nanofiber as carrier
Catalytic activity：Play spike potential and shift to an earlier date 100 millivolts than platinum carbon catalyst, platinum utilization reaches 80%；It is described to be received with porous carbon
Rice fiber is the durability of the platinum based catalyst of carrier：ECSA conservation rates reach 50% after 1000 circulations.
2. it is according to claim 1 it is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as carrier
Platinum based catalyst, it is characterised in that the average fibre diameter of the porous carbon nanofiber be 100~1000 nanometers, aperture
For 5~100 nanometers.
3. it is according to claim 1 it is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as carrier
Platinum based catalyst, it is characterised in that using porous carbon nanofiber as in the platinum based catalyst of carrier, the content of the platinum is
10wt%~40wt%.
4. it is according to claim 1 it is a kind of with high catalytic activity and high-durability using porous carbon nanofiber as carrier
Platinum based catalyst, it is characterised in that using porous carbon nanofiber as in the platinum based catalyst of carrier, the content of the carbon black
≤ 50wt%.
5. a kind of as described in any one of Claims 1 to 4 with high catalytic activity and high-durability with porous carbon Nanowire
The preparation method of the platinum based catalyst for carrier is tieed up, it is characterized in that：By porous carbon nanofiber and platinum carbon catalyst common distribution
In dispersant, dried after supersound process, that is, it is carrier using porous carbon nanofiber as load to obtain using porous carbon nanofiber
The platinum based catalyst of body.
6. preparation method according to claim 5, it is characterised in that the dispersant is isopropanol or methanol；The platinum
Platinum content is 15wt%~60wt% in Pd/carbon catalyst, and remaining is carbon black；20~40nm of particle diameter of the platinum carbon catalyst；It is described
It is ultrasonically treated and refers to handle 0.5~4 hour with 50 hertz of frequency ultrasound；The drying refers to dry 6 at a temperature of 40~120 DEG C
~12 hours.
7. use a kind of platinum based catalyst institute using porous carbon nanofiber as carrier as described in any one of Claims 1 to 4
Obtained monocell, it is placed between anode and cathode flow-field plate and is formed by membrane electrode assembly, it is characterized in that：The membrane electrode assembly be by with
Porous carbon nanofiber is sprayed at PEM cathode side for the platinum based catalyst of carrier and anode-side obtains through hot pressing；Film electricity
Pole component resistance value is 200-500 ohms.
8. monocell according to claim 7, it is characterised in that the amount of the spraying is 0.2-0.8mg-Pt/cm2；It is described
The temperature of hot pressing is 50-150 DEG C.
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