CN108063269B - It is a kind of using glassy metal as the fuel-cell catalyst of carrier and preparation method - Google Patents
It is a kind of using glassy metal as the fuel-cell catalyst of carrier and preparation method Download PDFInfo
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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 present invention relates to a kind of using glassy metal as the fuel-cell catalyst of carrier and preparation method, belongs to fuel cell catalyst technical field.The technical problem to be solved by the present invention is to provide a kind of using glassy metal as the fuel-cell catalyst of carrier.The catalyst includes glassy metal carrier and the metallic particles that is supported on glassy metal carrier, wherein the glassy metal carrier is zirconium-base alloy glassy metal, and the metallic particles is at least one of platinum, iron, cobalt, nickel, rhodium, palladium, iridium, gold, titanium；The partial size of the metallic particles is 5~800nm.Compared with existing catalyst carrier contains carbon or carbonaceous material, fuel-cell catalyst of the invention is using glassy metal as carrier, carbon is entirely free of in catalyst, it is not easy to the corrosion and aggregation of carrier occur, to improve the activity and endurance quality of catalyst.
Description
Technical field
The present invention relates to a kind of using glassy metal as the fuel-cell catalyst of carrier and preparation method, belongs to fuel cell
Catalyst technical field.
Background technique
Fuel cell is a kind of hair that the chemical energy of fuel and oxidant is directly changed into electric energy by electrochemical reaction
Electric installation.Mainly it is made of anode, cathode, electrolyte and ancillary equipment.Since fuel cell has, high-efficient, starting is fast, dirty
Contaminate the advantages that small, it is considered to be it is hopeful largely to provide the 4th kind of generation technology of electric energy after wind-force, waterpower and solar energy,
It is a kind of green energy resource technology, " energy shortage " and " environmental pollution " this two hang-up that the current world faces can be effectively relieved,
Realize the diversification of the energy.Proton Exchange Membrane Fuel Cells (PEMFC) belongs to low-temperature fuel cell, in addition to having fuel cell
It is general it is specific except, also have operating temperature is low, starting is fast, electroless liquid stream is lost, corrosion-free, energy transformation ratio is high, the service life is long,
The features such as light-weight, small in size is the ideal substitute electric power of portable power, distributed power station, the following electric car.
PEMFC generallys use hydrogen and oxygen (or hydrogen and air) as reaction gas.In order to accelerate electrochemical reaction
Speed all contains catalyst in gas-diffusion electrode.So far, the cathode of PEMFC and anode catalyst are still with platinum (Pt)
It is main.And fuel-cell catalyst carrier should have good electronics (or proton) conducting power, biggish specific surface area, reasonable
Pore structure and excellent corrosion resistance.Currently used catalyst carrier is carbon carrier.
Common platinum/C catalyst (being slightly written as Pt/C) although having many advantages, such as high-specific surface area and high conductivity,
Under PEMFC working environment, especially be but easy to corrode under the elevated oxygen level of cathode, high condition, chemistry and
Electrochemical stability is difficult to reach the life requirements of PEMFC.The corrosion of carbon carrier will cause serious consequence, be mainly manifested in:
The corrosion of carbon carrier will cause the removing between platinum grain and carrier, make platinum grain that can not obtain electronics and ineffective；Carbon carrier
Corrosion also will cause collapsing for platinum grain, make platinum grain generate aggregation, and the platinum grain collapsed be easier by carbon carrier
Covering or masking；The corrosion of carbon carrier can also change the surface state of material, it will usually reduce the hydrophobicity of material, increase gas
Body resistance to mass tranfer, at the same the intermediate product (such as CO) of oxidation of coal can also strong adsorption on the surface of platinum, cause catalyst poisoning.Cause
This, needs to improve catalyst of fuel batter with proton exchange film.
The electrode for disclosing a proton exchanging film fuel battery application No. is the patent of invention of 201611118005.X is urged
The carrier of agent easily hinders catalyst when solving the carrier supported catalyst that conventional carriers preparation process is complicated for operation, prepares
Service efficiency, easily cause the problem of catalyst poisoning, the carrier is by graphene and allyl glycidyl ether, H2SnCl6
After being reacted respectively with 4,4- diphthalic anhydrides, reaction product is reacted, finally with graphite oxide alkene reaction system
Obtain carrier solution.The carrier has good compatibility to catalyst, has good conducting effect, can effectively improve and urge
The catalytic activity of agent, preparation process is easy to operate, and preparation cost is low.
Application No. is 201510453350.8 patent of invention disclose it is a kind of using nano-cable as the fuel cell of carrier
Catalyst and preparation method thereof belongs to fuel cell catalyst technical field.The fuel-cell catalyst is carried in nano-cable
Unitary, binary or polynary noble metal active component are loaded on body and is formed, and wherein nano-cable carrier is with metal nano fibre
Dimension is core, the 1-dimention nano construction of cable that graphitic carbon is shell.The invention also discloses this using nano-cable as the fuel of carrier electricity
The preparation method of pond catalyst.The catalyst application range is wider, can include formic acid, methanol, ethyl alcohol, second two with catalysis oxidation
Small molecule acids and alcohols material including alcohol, glycerine, isopropanol, and there is excellent chemical property, therefore in matter
Have broad application prospects on proton exchange film fuel cell.
The carrier of the above patent is to use modified graphene or surface for the core-shell structure of graphene, carrier surface
Be carbons substance, still there is carbonaceous material it is perishable and aggregation, cause catalyst activity reduce durability be deteriorated lack
It falls into.
Summary of the invention
The corrosion and aggregation of carrier are easy to happen using carbonaceous or carbonaceous material as carrier for existing metal granular catalyst,
Catalyst activity is caused to reduce the defect that durability is deteriorated, the present invention proposes a kind of to urge by the fuel cell of carrier of glassy metal
Agent and preparation method.
First technical problem that the present invention solves is to provide a kind of using glassy metal as the fuel-cell catalyst of carrier.
The present invention is using glassy metal as the fuel-cell catalyst of carrier, including glassy metal carrier and is supported on metal glass
Metallic particles on glass carrier, wherein the glassy metal carrier be zirconium-base alloy glassy metal, the metallic particles be platinum,
At least one of iron, cobalt, nickel, rhodium, palladium, iridium, gold, titanium；The partial size of the metallic particles is 5~800nm.
The present invention is by making carrier for selection glassy metal, so that catalyst table in fuel battery negative pole oxygen reduction reaction
Reveal high activity and high stability, carrier is made using glassy metal, the aggregation of metallic when preventing temperature from increasing keeps lasting
Catalytic activity；It overcomes and carrier is made using carbon material, the corrosion of carbon carrier will cause the Severe aggregation of catalyst metal particles
The defect of failure improves the durability of fuel cell.
The advantages of glassy metal is also known as amorphous alloy, its existing metal and glass, and overcome their own disadvantage
Such as Glass breadks easily, without ductility.The intensity of glassy metal is higher than steel, and hardness is more than high hard tool steel, and has centainly tough
Property and rigidity, so, glassy metal is known as " king of glass " of " strike not broken, pound not rotten ".Most metal is while cooling
Will crystallization their atomic arrangement at well-regulated pattern be called lattice.But if crystallization does not occur, atom will be with
Machine arrangement, becomes glassy metal.And zirconium-base alloy is zirconium or the solid solution of other metals.Zirconium has low-down neutron absorption
Section, high rigidity, ductility and corrosion resistance.Using zirconium-base alloy glassy metal as the fuel-cell catalyst of carrier, make
The Severe aggregation of catalyst metal particles is caused to fail with that will not corrode in the process.
Preferably, the glassy metal carrier is zirconium copper base metal glass-film.
In order to improve the durability of fuel cell, inventor has found a kind of zirconium copper base metal glass-film of special component,
Chemical constituent is as follows: 10~30wt% of copper, 5~10wt% of nickel, 5~10wt% of aluminium, 1~5wt% of titanium, remaining is zirconium.As preferred side
The chemical constituent of case, the zirconium copper base metal glass-film is as follows: copper 20wt%, nickel 7wt%, aluminium 8wt%, titanium 3wt%, remaining is zirconium.
Second technical problem that the present invention solves is to provide a kind of using glassy metal as the fuel-cell catalyst of carrier
Preparation method.
The present invention includes the following steps: using glassy metal as the preparation method of the fuel-cell catalyst of carrier
A, under inert gas protection, metal melting is mixed, is then formed a film in the molten state, rapid cooling obtains
Glassy metal carrier；
B, metallic particles is welded or is embedded in glassy metal carrier surface using arc deposited or laser welding, it is then soft
Change and stretch, obtains the catalyst using glassy metal as carrier.
Wherein, mainly glassy metal carrier is prepared in a step, selects specific metal component, mixes after melting, at
Rapid cooling after film, so that metal does not crystallize in cooling procedure, glassy metal is can be obtained in metallic atom random alignment.
Since at high temperature, metal is easy by the dioxygen oxidation in air, and therefore, a step needs to carry out under inert gas protection, this
The invention inert gas refers to the gas not reacted with copper, nickel, aluminium, titanium, zirconium etc., for example, nitrogen, carbon dioxide, helium,
Neon, argon gas, Krypton, xenon or radon gas etc..
The temperature of melting is by metal molten, it is contemplated that the fusing point of metal zirconium is higher, is 1852 ± 2 DEG C, and metal
The boiling point of aluminium is lower, and only 2327 DEG C, it is preferred, therefore, that the temperature of a step metal melting is 1850~2000 DEG C.
The formation of rapid cooling and glassy metal is closely related, it is preferred that the cooling rate of the rapid cooling be 50~
80℃/s。
Metallic particles is welded or is embedded in glassy metal carrier surface by b step, used technique be arc deposited or
Laser welding.Wherein, arc deposited is vacuum cathode arc deposition, is commonly called as multi sphere plating.With ionization level height, ion current density
Greatly, ion flow power is high, and deposition rate is fast, and film-substrate cohesion is good, and using solid target, without molten bath, target can any position
Installation is set to guarantee the advantages that plated film is uniform, plating can also be reacted with deposited metal film, alloy film and synthesize various compound films
(nitride, carbide, oxide), it might even be possible to synthesize DLC film, CNx film etc., equipment operation is simple, and technology is easy to spread.
Preferably, the concrete operations of the arc deposited are as follows: metallic is packed into vacuum cathode arc depositing device
On, as cathode, glassy metal carrier is placed on the sample stage of vacuum cathode arc depositing device, glassy metal carrier and gold
The distance for belonging to particle is 2~10mm, is vacuumized to vacuum cathode arc depositing device, and when vacuum degree≤0.5 × 10-2Pa starts
Deposition, deposition process parameters are as follows: arc current is 70~90A, and 2~8A of coil current, sedimentation time is 10~20min.
Preferably, glassy metal carrier is 8mm, deposition process parameters are as follows: arc current at a distance from metallic
For 80A, coil current 5A, sedimentation time 15min.
Vacuum cathode arc depositing device commonly used in the art is suitable for the present invention.
Laser welding is a kind of high-efficiency and precision welding method using the laser beam of high-energy density as heat source.It welded
Journey category heat-conduction-type, i.e. laser emission heat workpiece surface, and surface heat is internally spread by heat transfer, by controlling laser
The parameters such as width, energy, peak power and the repetition rate of pulse, melt workpiece, form specific molten bath.
For welding, there are mainly two types of laser, i.e. CO2Laser and Nd:YAG laser.CO2Laser and Nd:YAG laser are all
It is the invisible infrared light of naked eyes.The light beam that Nd:YAG laser generates is mainly near infrared light, wavelength 1.06Lm, heat conductor pair
The absorptivity of this wavelength is higher, and for most of metal, its reflectivity is 20~30%.As long as using the light microscopic of standard
The light beam of near infrared band can be made to be focused to diameter 0.25mm.CO2The light beam of laser be far red light, wavelength 10.6Lm,
Most of metal reaches 80~90% to the reflectivity of this light, need special light microscopic light beam be focused into diameter be 0.75~
0.1mm.Nd:YAG laser power can generally reach 4000~6000W or so, and present maximum power has reached 10000W.And CO2
It is even more big that laser power can but easily reach 20000W.Both light sources are suitable for the present invention.
Preferably, in b step, the concrete operations of the laser welding are as follows: organic solvent being added into metallic, makes
It becomes paste, and paste-like metallic uniform particle is then coated in glassy metal carrier surface, forms 2~10 μm of metallic
Coating carries out laser welding after the organic solvent volatilization in metallic coating, and metallic is fixed on glassy metal and is carried
On body.
Laser welding apparatus commonly used in the art is suitable for the present invention.Not described in detail herein.
Common volatile organic solvent is suitable for the present invention, such as acetone, ethyl alcohol, methylene chloride, chloroform
Deng.In view of the cost and toxicity of organic solvent, it is preferred that the organic solvent is acetone or alcohol.
After metallic is fixed on glassy metal carrier by arc deposited or laser welding, need to carry out soft
Change and stretch, the activity and endurance quality of catalyst could be improved.The method that the softening stretches are as follows: load is had into metallic
Glassy metal carrier is warming up to 300~500 DEG C, and 10~30s is stretched under for the tensile strength of 100~200kPa.In this way
Softening stretch after, the performance of obtained fuel-cell catalyst is more preferable.
Softening is stretched and can be carried out on cupping machine, and high-temperature tensile testing machine commonly used in the art is suitable for this hair
It is bright.
The invention has the following beneficial effects:
Compared with existing catalyst carrier contains carbon or carbonaceous material, fuel-cell catalyst of the invention is with gold
Category glass is carrier, is entirely free of carbon in catalyst, it is not easy to the corrosion and aggregation that carrier occurs, to improve catalyst
Activity and endurance quality.In addition, the present invention is using glassy metal as the fuel-cell catalyst of carrier, preparation method is simple, work
Skill process is succinct, and preparation cost is lower, is applicable to industrialized production.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The fuel-cell catalyst using glassy metal as carrier is prepared with the following method:
A, the preparation of glassy metal carrier: under inert gas protection, metal is warming up to 1850 DEG C, melting mixes, so
It forms a film in the molten state afterwards, with 80 DEG C/s rapid cooling, obtains glassy metal carrier；Wherein, the glassy metal carrier
Chemical component is as follows: copper 10wt%, nickel 5wt%, aluminium 10wt%, titanium 5wt%, remaining is zirconium.
B, arc deposited: being that 5~800nm platinum particle is packed into vacuum cathode arc depositing device by partial size to be deposited
On, as cathode, glassy metal carrier is placed on the sample stage of vacuum cathode arc depositing device, glassy metal carrier and gold
The distance for belonging to particle is 10mm, is vacuumized to vacuum cathode arc depositing device, and when vacuum degree≤0.5 × 10-2Pa starts to sink
Product, deposition process parameters are as follows: arc current 70A, coil current 8A, sedimentation time 10min.
C, softening stretches: after arc deposited, there is the glassy metal carrier of metallic to be placed in cupping machine load,
300 DEG C are warming up to, 30s is stretched in the case where Rm is the tensile strength of 200kPa, obtains the catalyst using glassy metal as carrier.
This is subjected to durability evaluation by the catalyst of carrier of glassy metal.Its method is as follows:
Cyclic voltammetry (Cyclic voltammograms, CV test): in the sulfuric acid that temperature is 60 DEG C, concentration is 0.5M
It is carried out in solution, scanning area is 0.05V to 1.20V (vs RHE), sweep speed 50mV/s.Electro-chemical activity surface region
(electrochemical active surface area, ECSA) can be according to 0.05V to the 0.4V (vs RHE) on CV curve
Hydrogen desorption areal calculation obtain.
Accelerate experiment of degenerating: being 60 DEG C in temperature, carried out in the sulfuric acid solution that the concentration of oxygen saturation is 0.5M.0.8
Into the region of 1.30V vs RHE, multiple scanning in 45 hours is carried out with the sweep speed of 100mV/s.Accelerate experiment knot of degenerating
Shu Hou carries out CV test again.
The slip of the ECSA of the catalyst material for the experiment front and back that accelerates to degenerate is calculated, the result is shown in tables 1.
Embodiment 2
The fuel-cell catalyst using glassy metal as carrier is prepared with the following method:
A, the preparation of glassy metal carrier: under inert gas protection, metal is warming up to 2000 DEG C, melting mixes, so
It forms a film in the molten state afterwards, with 50 DEG C/s rapid cooling, obtains glassy metal carrier；Wherein, the glassy metal carrier
Chemical component is as follows: copper 30wt%, nickel 10wt%, aluminium 5wt%, titanium 1wt%, remaining is zirconium.
B, arc deposited: being that 5~800nm platinum particle is packed into vacuum cathode arc depositing device by partial size to be deposited
On, as cathode, glassy metal carrier is placed on the sample stage of vacuum cathode arc depositing device, glassy metal carrier and gold
The distance for belonging to particle is 2mm, is vacuumized to vacuum cathode arc depositing device, and when vacuum degree≤0.5 × 10-2Pa starts to deposit,
Deposition process parameters are as follows: arc current 90A, coil current 2A, sedimentation time 20min.
C, softening stretches: after arc deposited, there is the glassy metal carrier of metallic to be placed in cupping machine load,
500 DEG C are warming up to, 10s is stretched in the case where Rm is the tensile strength of 100kPa, obtains the catalyst using glassy metal as carrier.
Durability evaluation is carried out by the catalyst of carrier of glassy metal to this according to the method that embodiment 1 is recorded, is calculated
Accelerate to degenerate and test the slip of the ECSA of catalyst material of front and back, the result is shown in tables 1.
Embodiment 3
The fuel-cell catalyst using glassy metal as carrier is prepared with the following method:
A, the preparation of glassy metal carrier: under inert gas protection, metal is warming up to 1900 DEG C, melting mixes, so
It forms a film in the molten state afterwards, with 60 DEG C/s rapid cooling, obtains glassy metal carrier；Wherein, the glassy metal carrier
Chemical component is as follows: copper 18wt%, nickel 7wt%, aluminium 7wt%, titanium 3wt%, remaining is zirconium.
B, arc deposited: being that 5~800nm platinum particle is packed into vacuum cathode arc depositing device by partial size to be deposited
On, as cathode, glassy metal carrier is placed on the sample stage of vacuum cathode arc depositing device, glassy metal carrier and gold
The distance for belonging to particle is 8mm, is vacuumized to vacuum cathode arc depositing device, and when vacuum degree≤0.5 × 10-2Pa starts to deposit,
Deposition process parameters are as follows: arc current 80A, coil current 5A, sedimentation time 15min.
C, softening stretches: after arc deposited, there is the glassy metal carrier of metallic to be placed in cupping machine load,
400 DEG C are warming up to, 20s is stretched in the case where Rm is the tensile strength of 150kPa, obtains the catalyst using glassy metal as carrier.
Durability evaluation is carried out by the catalyst of carrier of glassy metal to this according to the method that embodiment 1 is recorded, is calculated
Accelerate to degenerate and test the slip of the ECSA of catalyst material of front and back, the result is shown in tables 1.
Embodiment 4
The fuel-cell catalyst using glassy metal as carrier is prepared with the following method:
A, the preparation of glassy metal carrier: under inert gas protection, metal is warming up to 1900 DEG C, melting mixes, so
It forms a film in the molten state afterwards, with 70 DEG C/s rapid cooling, obtains glassy metal carrier；Wherein, the glassy metal carrier
Chemical component is as follows: copper 23wt%, nickel 9wt%, aluminium 6wt%, titanium 4wt%, remaining is zirconium.
B, laser welding: it is that organic solvent ethyl alcohol is added in 5~800nm platinum particle toward partial size to be welded, makes it
As paste, paste-like metallic uniform particle is then coated in glassy metal carrier surface, forms 2 μm of metallic coating,
Laser welding is carried out after the organic solvent volatilization in metallic coating, metallic is fixed on glassy metal carrier.
C, softening stretches: after laser welding, there is the glassy metal carrier of metallic to be placed in cupping machine load,
400 DEG C are warming up to, 20s is stretched in the case where Rm is the tensile strength of 150kPa, obtains the catalyst using glassy metal as carrier.
Durability evaluation is carried out by the catalyst of carrier of glassy metal to this according to the method that embodiment 1 is recorded, is calculated
Accelerate to degenerate and test the slip of the ECSA of catalyst material of front and back, the result is shown in tables 1.
Embodiment 5
The fuel-cell catalyst using glassy metal as carrier is prepared with the following method:
A, the preparation of glassy metal carrier: under inert gas protection, metal is warming up to 1900 DEG C, melting mixes, so
It forms a film in the molten state afterwards, with 55 DEG C/s rapid cooling, obtains glassy metal carrier；Wherein, the glassy metal carrier
Chemical component is as follows: copper 15wt%, nickel 5wt%, aluminium 5wt%, titanium 3wt%, remaining is zirconium.
B, laser welding: it is that organic solvent-acetone is added in 5~800nm platinum particle toward partial size to be welded, makes it
As paste, paste-like metallic uniform particle is then coated in glassy metal carrier surface, forms 10 μm of metallic coating,
Laser welding is carried out after the organic solvent volatilization in metallic coating, metallic is fixed on glassy metal carrier.
C, softening stretches: after laser welding, there is the glassy metal carrier of metallic to be placed in cupping machine load,
400 DEG C are warming up to, 20s is stretched in the case where Rm is the tensile strength of 150kPa, obtains the catalyst using glassy metal as carrier.
Durability evaluation is carried out by the catalyst of carrier of glassy metal to this according to the method that embodiment 1 is recorded, is calculated
Accelerate to degenerate and test the slip of the ECSA of catalyst material of front and back, the result is shown in tables 1.
Embodiment 6
The fuel-cell catalyst using glassy metal as carrier is prepared with the following method:
A, the preparation of glassy metal carrier: under inert gas protection, metal is warming up to 1900 DEG C, melting mixes, so
It forms a film in the molten state afterwards, with 70 DEG C/s rapid cooling, obtains glassy metal carrier；Wherein, the glassy metal carrier
Chemical component is as follows: copper 20wt%, nickel 7wt%, aluminium 8wt%, titanium 3wt%, remaining is zirconium.
B, laser welding: it is that organic solvent ethyl alcohol is added in 5~800nm platinum particle toward partial size to be welded, makes it
As paste, paste-like metallic uniform particle is then coated in glassy metal carrier surface, forms 8 μm of metallic coating,
Laser welding is carried out after the organic solvent volatilization in metallic coating, metallic is fixed on glassy metal carrier.
C, softening stretches: after laser welding, there is the glassy metal carrier of metallic to be placed in cupping machine load,
400 DEG C are warming up to, 20s is stretched in the case where Rm is the tensile strength of 150kPa, obtains the catalyst using glassy metal as carrier.
Durability evaluation is carried out by the catalyst of carrier of glassy metal to this according to the method that embodiment 1 is recorded, is calculated
Accelerate to degenerate and test the slip of the ECSA of catalyst material of front and back, the result is shown in tables 1.
Comparative example 1
The fuel-cell catalyst using glassy metal as carrier is prepared with the following method:
A, the preparation of glassy metal carrier: under inert gas protection, metal is warming up to 1900 DEG C, melting mixes, so
It forms a film in the molten state afterwards, with 70 DEG C/s rapid cooling, obtains glassy metal carrier；Wherein, the glassy metal carrier
Chemical component is as follows: copper 20wt%, nickel 7wt%, aluminium 8wt%, titanium 3wt%, remaining is zirconium.
B, laser welding: it is that organic solvent ethyl alcohol is added in 5~800nm platinum particle toward partial size to be welded, makes it
As paste, paste-like metallic uniform particle is then coated in glassy metal carrier surface, forms 8 μm of metallic coating,
Laser welding is carried out after the organic solvent volatilization in metallic coating, metallic is fixed on glassy metal carrier,
Obtain the catalyst using glassy metal as carrier.
Durability evaluation is carried out by the catalyst of carrier of glassy metal to this according to the method that embodiment 1 is recorded, is calculated
Accelerate to degenerate and test the slip of the ECSA of catalyst material of front and back, the result is shown in tables 1.
Comparative example 2
Durability evaluation is carried out to common commercially available Pt/C catalyst according to the method that embodiment 1 is recorded, calculates and accelerates to move back
Change the slip of the ECSA of the catalyst material of experiment front and back, the result is shown in tables 1.
Table 1
| Number | ECSA slip (%) |
| Embodiment 1 | 12.3 |
| Embodiment 2 | 11.6 |
| Embodiment 3 | 8.4 |
| Embodiment 4 | 9.3 |
| Embodiment 5 | 8.5 |
| Embodiment 6 | 5.4 |
| Comparative example 1 | 16.4 |
| Comparative example 2 | 23.5 |
Claims (10)
1. a kind of using glassy metal as the fuel-cell catalyst of carrier, it is characterised in that: the catalyst includes that glassy metal carries
Body and the metallic particles being supported on glassy metal carrier, wherein the glassy metal carrier is zirconium-base alloy glassy metal, institute
Stating metallic particles is at least one of platinum, iron, cobalt, nickel, rhodium, palladium, iridium, gold, titanium；The partial size of the metallic particles be 5~
800nm；
The catalyst is prepared by following methods:
A, under inert gas protection, metal melting is mixed, is then formed a film in the molten state, rapid cooling obtains metal
Glass carrier；
B, metallic particles is welded or is embedded in glassy metal carrier surface using arc deposited or laser welding, then softening is drawn
It stretches, obtains the catalyst using glassy metal as carrier.
2. according to claim 1 using glassy metal as the fuel-cell catalyst of carrier, it is characterised in that: the metal
Glass carrier is zirconium copper base metal glass-film.
3. according to claim 2 using glassy metal as the fuel-cell catalyst of carrier, it is characterised in that: the zirconium copper
The chemical constituent of base metal glass film is as follows: 10~30wt% of copper, 5~10wt% of nickel, 5~10wt% of aluminium, 1~5wt% of titanium, remaining is
Zirconium.
4. according to claim 3 using glassy metal as the fuel-cell catalyst of carrier, it is characterised in that: the zirconium copper
The chemical constituent of base metal glass film is as follows: copper 20wt%, nickel 7wt%, aluminium 8wt%, titanium 3wt%, remaining is zirconium.
5. according to claim 1 using glassy metal as the fuel-cell catalyst of carrier, it is characterised in that: in a step,
The temperature of metal melting is 1850~2000 DEG C.
6. the fuel-cell catalyst that glassy metal according to claim 1 is carrier, it is characterised in that: in a step, institute
The cooling rate for stating rapid cooling is 50~80 DEG C/s.
7. the fuel-cell catalyst that glassy metal according to claim 1 is carrier, it is characterised in that: in b step, institute
The concrete operations for stating arc deposited are as follows: metallic being packed on vacuum cathode arc depositing device, as cathode, by metal
Glass carrier is placed on the sample stage of vacuum cathode arc depositing device, glassy metal carrier at a distance from metallic for 2~
10mm vacuumizes vacuum cathode arc depositing device, vacuum degree≤0.5 × 10-2 Start to deposit when Pa, deposition process parameters
Are as follows: arc current is 70~90A, and 2~8A of coil current, sedimentation time is 10~20min.
8. the fuel-cell catalyst that glassy metal according to claim 1 is carrier, it is characterised in that: in b step, institute
The concrete operations for stating laser welding are as follows: organic solvent being added into metallic, becomes paste, then by paste-like metallic
Uniform particle is coated in glassy metal carrier surface, 2~10 μm of metallic coating is formed, to having in metallic coating
Laser welding is carried out after solvent volatilization, metallic is fixed on glassy metal carrier.
9. the fuel-cell catalyst that glassy metal according to claim 8 is carrier, it is characterised in that: described organic molten
Agent is acetone or alcohol.
10. the fuel-cell catalyst that glassy metal according to claim 1 is carrier, it is characterised in that: in b step,
The method that the softening stretches are as follows: there is the glassy metal carrier of metallic to be warming up to 300~500 DEG C load, 100~
10~30s is stretched under the tensile strength of 200kPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711470300.6A CN108063269B (en) | 2017-12-29 | 2017-12-29 | It is a kind of using glassy metal as the fuel-cell catalyst of carrier and preparation method |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007066817A (en) * | 2005-09-01 | 2007-03-15 | Japan Science & Technology Agency | Separator for solid polymer fuel cell, and manufacturing method of the same |
| CN101084056A (en) * | 2004-11-15 | 2007-12-05 | 日矿金属株式会社 | Hydrogen separation membrane, sputtering target for forming of hydrogen separation membrane, and process for producing the same |
| CN102779575A (en) * | 2012-07-26 | 2012-11-14 | 重庆师范大学 | Metal wire for improving strength and corrosion resistance and preparation method thereof |
| CN103153502A (en) * | 2010-08-31 | 2013-06-12 | 加利福尼亚技术学院 | High aspect ratio parts of bulk metallic glass and methods of manufacturing thereof |
| CN105413679A (en) * | 2015-11-05 | 2016-03-23 | 湖南工业大学 | Preparation method of graphene and two-dimensional noble metal cluster composite material |
| CN106972178A (en) * | 2016-01-08 | 2017-07-21 | 福特全球技术公司 | Calalyst layer of fuel cell and forming method thereof and the fuel cell including it |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101247410B1 (en) * | 2004-03-25 | 2013-03-25 | 가부시키가이샤 토호쿠 테크노 아치 | Metallic glass laminate, process for producing the same and use thereof |
| JP2006252854A (en) * | 2005-03-09 | 2006-09-21 | Dainatsukusu:Kk | Manufacturing method for metallic glass separator |
| CN102364738B (en) * | 2011-11-15 | 2013-05-08 | 大连交通大学 | Polymeric electrolyte membrane fuel cell bulk metallic glass bipolar plate and manufacturing method thereof |
| CN102899592B (en) * | 2012-10-19 | 2014-09-17 | 南京理工大学 | Plastic zirconium-based metal glass and preparation method thereof |
| US9178220B2 (en) * | 2013-02-01 | 2015-11-03 | Ford Global Technologies, Llc | Catalyst assembly including an intermetallic compound of iridium and tungsten |
-
2017
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084056A (en) * | 2004-11-15 | 2007-12-05 | 日矿金属株式会社 | Hydrogen separation membrane, sputtering target for forming of hydrogen separation membrane, and process for producing the same |
| JP2007066817A (en) * | 2005-09-01 | 2007-03-15 | Japan Science & Technology Agency | Separator for solid polymer fuel cell, and manufacturing method of the same |
| CN103153502A (en) * | 2010-08-31 | 2013-06-12 | 加利福尼亚技术学院 | High aspect ratio parts of bulk metallic glass and methods of manufacturing thereof |
| CN102779575A (en) * | 2012-07-26 | 2012-11-14 | 重庆师范大学 | Metal wire for improving strength and corrosion resistance and preparation method thereof |
| CN105413679A (en) * | 2015-11-05 | 2016-03-23 | 湖南工业大学 | Preparation method of graphene and two-dimensional noble metal cluster composite material |
| CN106972178A (en) * | 2016-01-08 | 2017-07-21 | 福特全球技术公司 | Calalyst layer of fuel cell and forming method thereof and the fuel cell including it |
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