CN109599580A - A kind of ultra-thin membrane electrode and its preparation method and application for neat liquid fuel cell - Google Patents
A kind of ultra-thin membrane electrode and its preparation method and application for neat liquid fuel cell Download PDFInfo
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- CN109599580A CN109599580A CN201811578978.0A CN201811578978A CN109599580A CN 109599580 A CN109599580 A CN 109599580A CN 201811578978 A CN201811578978 A CN 201811578978A CN 109599580 A CN109599580 A CN 109599580A
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- H01—ELECTRIC ELEMENTS
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
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- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
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- H01M4/90—Selection of catalytic material
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Abstract
The present invention is a kind of ultra-thin membrane electrode and its preparation method and application for neat liquid fuel cell.The composition of the membrane electrode is followed successively by anode support, anode catalyst layer, amberplex, cathode catalysis layer and cathode support layers；The anode support and cathode support layers is carbon paper or carbon cloth, and the anode catalyst layer is porous metals alloy firm；The cathode catalysis layer is negative the porous metallic layers of carrying active component.The present invention is conducive to the advantage of transmitting substance, electronics and high-specific surface area using porous metals alloy firm or porous golden Supported Pt Nanoparticles, solves the structure problem of high density and high-permeability and the problem of materials of high activity and high stability to a certain extent.
Description
Technical field
The ultra-thin membrane electrode and preparation method thereof that the present invention relates to a kind of for neat liquid fuel cell, specifically, relating to
And a kind of preparation for constructing ultra-thin membrane electrode and membrane electrode as Catalytic Layer using porous metals or porous metals alloy firm
Method.
Background technique
The huge energy resource system set up in 20th century can not adapt to future society to efficiently, it is cleaning, economical, safety
Energy system requirement, so studying efficient, the clean new energy system of one kind is the important channel to solve the above problems.Fuel
Battery is a kind of power generation dress that the chemical energy being stored in fuel and oxidant is converted into electric energy by electrochemical reaction
It sets.Because the conversion of its energy is not limited by Carnot cycle, and product is substantially pollution-free to environment, has vast potential for future development.
Compared with other kinds of fuel cell, the neat liquid fuel cell originating from Proton Exchange Membrane Fuel Cells is widely closed
Note, fuel such as methanol, formic acid, hydrazine, sodium borohydride for neat liquid anode of fuel cell etc. have specific energy height, theoretical open circuit
Current potential is high, is easy to transport the advantage of storage, the hydrogen peroxide oxidant for neat liquid fuel battery negative pole have reaction rate it is fast,
The high advantage of theoretical reaction potential, therefore, neat liquid fuel cell are the best times as portable power and mobile power supply
Choosing.
The catalyst of conventional fuel cell membrane electrode is mostly carbon load type fine catalyst, i.e., active component is with nano particle
Form is supported in high-specific surface area carbon support material.On the one hand in carbon supported catalyst, between active component and carrier only
There are physisorptions, and active component nanoparticle is easy in carrier surface migration, reunites and grow up in use, make
It is reduced at catalyst activity surface area, and then leads to fuel cell membrane electrode performance is gradually reduced in use, worked the longevity
Life shortening, reliability decrease.On the other hand, fine catalyst need to be with the nafion tree of leading proton when using as electrode material
Rouge, conductive son carbon dust mixing after spray on the carbon paper with laminar microporous diffuser, catalyst granules must with lead proton body, lead
Electron contacts could conduct the proton generated in reaction and electronics simultaneously, and therefore, which is easy to cause part to urge
Catalyst particles and nafion resin or carbon dust poor contact cannot play effectiveness, and cause the loading of catalyst higher, cost mentions
It rises.
Membrane electrode is the core component of fuel cell, and the membrane electrode of traditional handicraft preparation is 7 layers of structure, specific connection side
Formula is that layer is placed in the middle centered on amberplex, and two sides are followed successively by Catalytic Layer, laminar microporous diffuser and supporting layer from inside to outside；Wherein urge
Change the electrochemical reaction generation place that layer is oxidized and oxidant reduction；Laminar microporous diffuser has important liquid/gas management
Function, the laminar microporous diffuser with appropriate specific surface area and pore volume can be effectively improved the biography of liquids and gases in fuel cell
It passs, reduces battery in the concentration polarization of high current density region, the membrane electrode laminar microporous diffuser and Catalytic Layer of traditional handicraft preparation are total
Thickness value is larger, and total thickness reaches 100 μm~200 μm.Excessive thickness can be such that volumetric power density reduces, thus shadow
Ring the application of commercializing fuel cells.
Summary of the invention
It is an object of the invention to be directed to the above-mentioned prior art, a kind of ultrathin membrane of neat liquid fuel cell is provided
Electrode and preparation method thereof.The material is straight based on " porous metals alloy firm " or " porous metals load active component "
Connect the ultra-thin membrane electrode of 5 layers of structure of preparation.In preparation process, by suitable sputtering parameter, ternary alloy three-partalloy is obtained, and then pass through
Alkali liquid corrosion method obtains anode catalyst layer；Electrum corrosion is prepared by porous gold by acid solution again, and then is steamed using hydrazine
The platinum ion that gas reduction is attached on porous gold obtains cathode catalysis layer.The present invention utilizes porous metals alloy firm or porous
Golden Supported Pt Nanoparticles possess the metal ligament of co-continuous and the advantage in hole, including continuous metal ligament provides quick electronic conductivity
Energy, continuous hole can be used as unobstructed mass transfer channel, the metal ligament of high-specific surface area provides sufficient chemical reaction site,
The dual function that Catalytic Layer and laminar microporous diffuser in conventional powder type catalyst preparation membrane electrode are realized with this, by membrane electrode knot
Structure is reduced to 5 layers by 7 layers, while promoting membrane electrode area power density, reduces membrane electrode thickness, further increases neat liquid
The volumetric power density of fuel cell.
Realization that the present invention adopts the following technical solutions:
A kind of ultra-thin membrane electrode for neat liquid fuel cell, the composition of the membrane electrode are followed successively by anode support, sun
Pole Catalytic Layer, amberplex, cathode catalysis layer and cathode support layers；
The anode support is identical with cathode support layers, is carbon paper or carbon cloth, with a thickness of 100~200 μm；
The anode catalyst layer is porous metals alloy firm, with a thickness of 0.02~1 μm；Aperture is 0.02~0.1 μm.
The amberplex is cation-exchange membrane or anion-exchange membrane, with a thickness of 25~300 μm；
The cation-exchange membrane is Nafion membrane, and the anion-exchange membrane is AMI film；
The cathode catalysis layer is negative the porous metallic layers of carrying active component, and with a thickness of 0.02~1 μm, aperture is
0.02~0.1 μm；Porous metals are gold, and active component is platinum, and the load capacity of platinum is 180 μ g/cm2~220 μ g/cm2。
The porous metals alloy firm is to obtain after chemical attack removes aluminum metal in the ternary alloy three-partalloy containing aluminium
Substance, aperture are 0.02~0.1 μm；The ternary alloy three-partalloy containing Al be selected from the ternary alloy three-partalloy containing PtAl, the ternary alloy three-partalloy containing PdAl,
One of ternary alloy three-partalloy containing AuAl；The atomic molar percentage that Al atom accounts for ternary alloy containing Al is 30%~70%.
The PtAl ternary alloy three-partalloy is PtRuAl, PtSnAl, PtBiAl or PtPbAl；The ternary containing PdAl is closed
Gold is PdCuAl or PdNiAl；The ternary alloy three-partalloy containing AuAl is AuCuAl or AuPtAl.
The porous metals are that will obtain after component removal active in the bianry alloy for containing gold；
The bianry alloy containing gold is specially electrum, and golden atomic molar percentage is 40%~60%.
The preparation method of the ultra-thin membrane electrode for neat liquid fuel cell, comprising the following steps:
(1) amberplex is sequentially placed into hydrogenperoxide steam generator and dilution heat of sulfuric acid under conditions of 60 DEG C~100 DEG C
In, respectively boil 0.5h~1.5h；The amberplex with a thickness of 25 μm~300 μm；The hydrogenperoxide steam generator it is dense
Degree range is 3wt%~5wt%；The dilute sulfuric acid concentration is 0.5M~1M；
(2) in high vacuum dual chamber magnetic control sputtering system, ternary is sputtered in the ion exchange film surface that upper step obtains and is closed
Gold, time are 1min~3min；The ternary alloy three-partalloy of sputtering with a thickness of 0.02~1 μm；
(3) " ternary alloy three-partalloy-amberplex " material that upper step obtains is put into the sodium hydroxide lye of 1M~3M rotten
For 24 hours~48h is lost, corresponding anode catalyst layer and ion exchange membrane material are obtained；
(4) by the electrum of 0.02~1 μ m-thick in the nitric acid of 65wt%~68wt%, 20 DEG C~40 DEG C of at a temperature of corruption
40min~80min is lost to obtain porous gold；Separately with lye by the pH value adjustment of 1mM~2mM platinum acid chloride solution to 9~10, and will
The temperature of reaction system maintains 20 DEG C~30 DEG C, and then obtained porous gold is put into platinum acid chloride solution, uses hydrazine solution
Platinum ion of the hydrazine steam reduction adsorption of generation on porous gold, reaction 30min~90min obtain the porous gold load of film-form
Platinum needs to fish for porous golden Supported Pt Nanoparticles with cathode carbon paper after the completion of preparation；
The platinum content supported on the porous gold is 180 μ g/cm2~220 μ g/cm2；The volume ratio of hydrazine solution is by " hydration
Hydrazine: water=1~2:1 " is obtained by mixing；
(5) hot pressing temperature of hot press and hot pressing pressure are adjusted to 120 DEG C~150 DEG C and 80kg/cm respectively first2~
120kg/cm2, then with fixture, successively general " urge by anode carbon paper, anode catalyst layer, amberplex, cathode from anode to cathode
Change layer and cathode carbon paper " it clips together and is put on hot press, it should be noted that anode carbon paper and cathode carbon paper must be stringent
Alignment, finally controlling hot pressing time is 120~240s；Obtain ultra-thin membrane electrode.
The application of the ultra-thin membrane electrode for neat liquid fuel cell is used for neat liquid fuel cell.
The neat liquid fuel cell is specially hydrazine hydrate-hydrogen peroxide as fuel battery, sodium borohydride-hydrogen peroxide as fuel electricity
Pond, methanol-hydrogen peroxide as fuel battery or formic acid-hydrogen peroxide fuel cell.
Membrane electrode thickness prepared by the present invention is about 60%~65% that traditional handicraft prepares membrane electrode thickness, and " yin-yang
The two poles of the earth platinum carrying capacity " or " single cathode platinum carrying capacity " are that traditional handicraft prepares the 50% of membrane electrode platinum carrying capacity hereinafter, and it is maximum
Power density is near or above the membrane electrode of traditional handicraft preparation.
Substantive distinguishing features of the invention are as follows:
Ultra-thin membrane electrode prepared by the present invention has 5 layers of structure, and connection type is placed in the middle for layer centered on amberplex, and two
Side is followed successively by Catalytic Layer and supporting layer from inside to outside；Centered on the amberplex of layer can be obtained by commercially available buying pattern,
According to the different selection cation-exchange membranes or anion-exchange membrane of anode fuel；" porous metals alloy as Catalytic Layer
Film " or " porous metallic layers load active component ", thickness range are 0.02~1 μm, than the film electricity of traditional handicraft production
Low 2~4 orders of magnitude in extremely corresponding part；Carbon paper or carbon cloth as supporting layer can also be obtained by commercially available buying pattern
?.Ultra-thin membrane electrode prepared by the present invention is traditional handicraft 50% hereinafter, and maximum work in anode or cathod catalyst carrying capacity
Rate density is near or above the membrane electrode maximum power density of traditional handicraft preparation.
The beneficial effects of the present invention are:
Porous metals alloy firm in anode assemblies of the present invention is capable of providing good mass transfer channel, porous metals alloy
The ligament of film both can be used as catalyst, can also be used as conductive daughter, and the thickness range of anode catalyst layer is 0.02~1 μ
M, 2~4 orders of magnitude smaller than the membrane electrode opposite position of traditional handicraft production.Amberplex can provide it is unobstructed from
Sub- transmission channel, porous metals alloy firm are embedded in the amberplex of ionic conductivity.It is generated in electrochemical reaction
Electronics can carbon paper by ligament and as anode support perhaps carbon cloth is quickly transferred to the proton or hydrogen of external circuit generation
Oxygen radical ion etc. can be transferred to cathode by the ion transmission channel of amberplex.Porous gold in cathode assembly can also mention
For good mass transfer channel, being attached to the tough platinum taken of porous gold as catalyst has biggish reactivity area.Cathode
The thickness range of Catalytic Layer is 0.02~1 μm, than membrane electrode opposite position also small 2~4 quantity of traditional handicraft production
Grade.The electronics generated in electrochemical reaction can pass through the carbon paper or carbon cloth and cathode porous as cathode support layers from external circuit
Gold is transferred on cathode platinum.Anode catalyst layer and cathode catalysis layer are a kind of macro-scale metals with three-dimensional continuous structure
Functional material.The performance and working life of the ultra-thin membrane electrode of neat liquid fuel cell of the method preparation are above traditional handicraft system
The membrane electrode of work.In embodiment 9,10,11,12, the catalyst usage amount at ultra-thin membrane electrode yin-yang the two poles of the earth is traditional handicraft
50% hereinafter, and maximum power be near or above traditional handicraft manufacture membrane electrode performance.In embodiment 13,14,15,16
In, the catalyst usage amount of ultra-thin membrane electrode cathode is the 50% of traditional handicraft hereinafter, and maximum power is more than traditional handicraft system
The membrane electrode performance made illustrates that preparation method provided by the invention can give full play to the performance of material.The film electricity of preparation simultaneously
It is great to have superthin structure advantage, the volumetric power density of fuel cell can be increased substantially.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings and also belong to protection scope of the present invention.
Fig. 1 is the transmission electron microscope for the ultra-thin membrane electrode cathode catalyst of neat liquid fuel cell that embodiment 1 obtains
Figure；Wherein, Figure 1A is the low resolution transmission electron microscope figure of porous golden Supported Pt Nanoparticles, and Figure 1B is the high score of porous golden Supported Pt Nanoparticles
Resolution transmission electron microscope figure；
Fig. 2 is the behaviour for the porous golden Supported Pt Nanoparticles of the ultra-thin membrane electrode cathode catalyst of neat liquid fuel cell that embodiment 1 obtains
Make schematic diagram；Wherein, vessel A fills platinum ion and porous gold；Vessel B fills hydrazine hydrate solution to generate hydrazine hydrate steam；
Fig. 3 is the structural schematic diagram for the ultra-thin membrane electrode of neat liquid fuel cell that embodiment 1 obtains；Wherein, A is anode branch
Support layer carbon paper or carbon cloth；B is porous metals alloy firm；C is amberplex, and wherein B is embedded on C；D is porous gold
Supported Pt Nanoparticles；E is cathode support layers carbon paper or carbon cloth.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The preparation of the neat liquid fuel cell membrane electrode of the embodiment of the present invention is specifically described below.
Neat liquid fuel cell membrane electrode anode catalyst layer preparation method is embedded ternary containing Al in ion exchange film surface and closes
Gold removes the Al atom in ternary alloy three-partalloy containing Al.
Porous metals alloy firm in anode assemblies is capable of providing good mass transfer channel, porous metals alloy firm
Ligament both can be used as catalyst, can also be used as conductive daughter.Amberplex can provide unobstructed ion transmission channel,
Porous metals alloy firm is embedded in the amberplex of ionic conductivity.The electronics generated in electrochemical reaction can be by tough
Band and carbon paper as anode support perhaps carbon cloth be quickly transferred to proton or hydroxide ion of external circuit generation etc. can
Cathode is transferred to by the ion transmission channel of amberplex.
Alloy containing Al is ternary alloy three-partalloy containing Al.After the Al removal in ternary alloy three-partalloy containing Al, porous metals alloy is obtained
Film, the present invention in as anode catalyst layer porous metals alloy firm to the anodes such as methanol, formic acid, hydrazine, sodium borohydride combustion
Material all has preferable catalytic effect.
Ternary alloy three-partalloy containing Al is in the ternary alloy three-partalloy containing PtAl, the ternary alloy three-partalloy containing PdAl and the ternary alloy three-partalloy containing AuAl
One kind.Ternary alloy three-partalloy containing PtAl may is that PtRuAl, PtSnAl, PtBiAl or PtPbAl；Ternary alloy three-partalloy containing PdAl can
To be: PdCuAl or PdNiAl；Ternary alloy three-partalloy containing AuAl may is that AuCuAl or AuPtAl.After removing Al atom, obtain
Porous metals alloy firm be PtRu, PtSn, PtBi, PtPb, PdCu, PdNi, AuCu or AuPt.
In alloy containing Al, the quantity of Al atom accounts for the 30-70% of the total atom number amount of the alloy containing Al.In alloy containing Al,
After removing Al atom, the porous metal film that aperture is 0.02~1 μm can be obtained.Make the neat liquid fuel electricity finally obtained
The activity and stability of pond membrane electrode anode catalyst layer are higher.
Optionally, as the selection of the porous metals alloy firm of neat liquid fuel cell membrane electrode anode catalyst layer with it is pure
The type of fuel liquid battery anode fuel is related.Porous metals alloy firm can be selected from PtRu, PtSn, PtBi, PtPb,
Any one in PdCu, PdNi, AuCu and AuPt.If formic acid solution, methanol solution are fired as neat liquid anode of fuel cell
When material, porous metals alloy firm can be selected from any one in PtRu, PtSn, PtBi and PtPb.If hydrazine solution, sodium borohydride
When solution is as neat liquid anode of fuel cell fuel, porous metals alloy firm be can be selected from PdCu, PdNi, AuCu and AuPt
Any one.
Being embedded ternary alloy three-partalloy containing Al in ion exchange film surface includes: using amberplex as substrate, using magnetron sputtering
Method sputters ternary alloy three-partalloy containing Al in ion exchange film surface.Alloy can be embedded to the table in the amberplex of ionic conductivity
Face, to obtain neat liquid fuel cell membrane electrode anode catalyst layer structure.
Optionally, using amberplex as substrate material, control underlayer temperature is the glassy state temperature of amberplex, is made
Substrate softens but cannot flow, with certain elasticity when touching, according to the difference of neat liquid anode of fuel cell fuel
Corresponding three kinds of metal targets are selected, Al ternary alloy three-partalloy will be contained using magnetron sputtering method is splashed to ion exchange film surface and be formed
Alloy-ion exchange membrane material.Magnetron sputtering apparatus used is high vacuum dual chamber magnetic control sputtering system.
Ternary alloy three-partalloy containing Al is selected from any one of PtRuAl, PtSnAl, PtBiAl and PtPbAl；It is with amberplex
Substrate makes its softening to silicon, sputters ternary alloy three-partalloy containing Al in ion exchange film surface using magnetron sputtering method.It obtains pure
Fuel liquid battery membrane electrode anode catalyst layer structure, can be used formic acid solution, methanol solution as anode fuel.
Any one of ternary alloy three-partalloy containing Al in PdCuAl, PdNiAl, AuCuAl and AuPtAl；With amberplex
For substrate, its softening is made to silicon, ternary alloy three-partalloy containing Al is sputtered in ion exchange film surface using magnetron sputtering method.It obtains
Neat liquid fuel cell membrane electrode anode catalyst layer structure, can be used hydrazine solution, sodium borohydride solution as anode fuel.
Further, in preferred embodiments of the present invention, removing the Al atom in ternary alloy three-partalloy containing Al includes: to hand in ion
It changes film surface and is embedded ternary alloy three-partalloy containing Al and be placed in aqueous slkali.Al in aqueous slkali and alloy occurs chemical reaction and enters solution
In, remove Al in alloy-layer all, to obtain porous metals alloy firm, and porous metals alloy firm be embedded from
In the conductive amberplex of son.
Further, in preferred embodiments of the present invention, alloy-ion exchange membrane material is placed on 1~3mol/L's
Al in ternary alloy three-partalloy is removed, obtains porous metals alloy firm by 24~48h in sodium hydroxide solution.
The preparation method of neat liquid fuel cell membrane electrode cathode catalysis layer.In neat liquid fuel cell, dioxygen is selected
Aqueous solution is as cathode oxidant, and neat liquid fuel cell electric discharge performance is influenced smaller by mass transfer at this time.In reality of the invention
It applies in example, the porous golden Supported Pt Nanoparticles as neat liquid fuel cell membrane electrode cathode catalysis layer are to the catalytic activity of hydrogen peroxide and steady
It is qualitative higher.
Further, in preferred embodiments of the present invention, by the commercial electrum of 0.4 μ m-thick be put into 65wt%~
68wt% is analyzed in the nitric acid of pure rank.Corrode 60 minutes under conditions of 30 DEG C.It is more with sheet glass taking-up after to the reaction time
Hole gold sample simultaneously cleans into the water, and so in triplicate, remaining nitric acid on porous golden sample can be washed substantially.
Further, in preferred embodiments of the present invention, the H of 1.93mM is taken2PtCl6Plating solution will be plated with sodium hydroxide solution
The pH value of liquid is accurately adjusted to 9.Porous golden sample is put into platinum plating solution at this time.Separately take vessel B.Platinum plating solution and porous will be filled
The vessel A of golden sample is put into vessel B and closes the lid, and the temperature of reaction system is maintained 25 DEG C.Finally utilize hydrazine hydrate
Platinum ion of the steam reduction adsorption on porous gold.The reaction time of platinum plating is 60 minutes.After reaction time, clean repeatedly
Porous gold Supported Pt Nanoparticles are three times to remove wherein remaining impurity.Porous gold Supported Pt Nanoparticles pass through high resolution transmission electron microscope hand
It is 3~7nm or so that section, which measures its platinum grain size,.Its platinum is tested with EDX8000 energy dispersion type x-ray fluorescence analyzer to support
Amount is 180~220 μ g/cm2.This operation is relatively simple, can realize continuous control by changing reaction time and bath concentration
The loading of platinum processed.
Further, in preferred embodiments of the present invention, the carbon paper of 100 μ m-thicks or carbon cloth are cut into 1cm2Size
Then carbon paper or carbon cloth are put into the sulfuric acid solution of 2M by area, boil 2h under conditions of 80 DEG C, its hydrophiling is located in advance
Reason.
Further, in preferred embodiments of the present invention, carbon paper or carbon cloth as cathode support layers are needed toward its back
Cohesiveness of the Nafion ethanol solution that mass fraction is 0.5% to improve carbon paper or carbon cloth is added dropwise in face.Be conducive to directly fish out
Take cathode of the porous golden Supported Pt Nanoparticles as the ultra-thin membrane electrode of neat liquid fuel cell.Because porous gold Supported Pt Nanoparticles are one layer and swim in
Film on the water surface fishes for porous golden Supported Pt Nanoparticles with carbon paper, and make the uniform corrugationless of porous golden Supported Pt Nanoparticles is laid in carbon paper one side
On, carbon paper is cathode support layers, and porous gold is cathode catalysis layer, and cathode assembly can be directly obtained after fishing in this way.
Further, in preferred embodiments of the present invention, amberplex is cut into the area of 3cm × 3cm first.So
Afterwards film be put into 80 DEG C, mass fraction be 3%~5% hydrogenperoxide steam generator in boil 1h.Then film is put into 80 DEG C, deionization
1h is boiled in water.Then film is put into 80 DEG C, boils 1h in the sulfuric acid solution of 0.5M.Finally film is put into 80 DEG C of deionized water and is boiled
1h.This pretreated purpose is to remove the metal ion and organic matter on amberplex.
" porous gold Supported Pt Nanoparticles " or " porous metals alloy in the Catalytic Layer of neat liquid fuel cell membrane electrode yin-yang the two poles of the earth
Film " all has duct.Its duct and ligament are continuous structure.The hole being connected in porous gold or porous metals alloy firm
Road is capable of providing good mass transfer channel.And electrochemical reaction generate electronics can by continuous ligament fast transfer,
Proton or hydroxide ion of generation etc. can rapidly be shifted by the ion transmission channel of ion-conducting polymers, further
The utilization efficiency for improving catalyst, effectively improves battery efficiency.
The aperture in duct is 0.02~0.1 μm, is remarkably improved the reactivity site of catalyst, keeps fuel cell membranes electric
The performance and working life of pole are promoted.The Catalytic Layer thickness range of neat liquid fuel cell membrane electrode is 0.02~1 μm, can be effective
Improve the volumetric power density of neat liquid fuel cell.
Further, in preferred embodiments of the present invention, amberplex is placed in the middle, as the porous of anode catalyst layer structure
Emtal alloy film is embedded the anode-side in amberplex, and outer is the carbon paper or carbon cloth as anode support.As
The porous golden Supported Pt Nanoparticles of cathode catalysis layer structure are connected to the cathode side of amberplex, and outer is the carbon as cathode support layers
Paper or carbon cloth, it is pointed out that cathode catalysis layer structure is fished on cathode support layers carbon paper or carbon cloth.Cause
It is one layer of film swum on the water surface for porous golden Supported Pt Nanoparticles, fishes for porous golden Supported Pt Nanoparticles with carbon paper, make porous golden Supported Pt Nanoparticles
Uniform corrugationless is laid in carbon paper one side, and carbon paper is cathode support layers, and porous gold is cathode catalysis layer, straight after fishing in this way
It connects to obtain cathode assembly.
It further, is 135 DEG C in hot pressing temperature in preferred embodiments of the present invention, hot pressing pressure 100kg/cm2,
Hot pressing time prepares the ultra-thin membrane electrode of neat liquid fuel cell under conditions of being 180s.
Amberplex of the present invention is cation-exchange membrane or anion-exchange membrane；The cation-exchange membrane
For Nafion membrane ", the anion-exchange membrane is AMI film；
Carbon paper or carbon cloth of the present invention are well known materials, and it is the dedicated import of fuel cell that following embodiment, which uses,
Carbon paper, thickness are 100 μm, and aperture is greater than 0.05 μm.
Embodiment 1
The first step is pre-processed to corresponding amberplex.In embodiment 1, it will be handed over a thickness of 127 μm of cation
Change the size that film (Nafion115) is cut into 3cm × 3cm size.First film be put into 80 DEG C, mass fraction be 3%~5%
1h is boiled in hydrogenperoxide steam generator to remove the organic matter in membrane removal.Then by film is put into 80 DEG C, to boil 1h in deionized water residual to remove
The hydrogenperoxide steam generator stayed.Then by film be put into 80 DEG C, boil 1h in the sulfuric acid solution of 0.5M with the foreign metal that goes in membrane removal from
Son.Finally film is put into 80 DEG C of deionized water and boils 1h to remove remaining sulfuric acid solution.
Second step is to prepare corresponding " alloy-amberplex " material.In embodiment 1, first base material 3cm
The Nafion115 film of × 3cm is fixed on specimen holder, and Nafion115 film is made to expose the area of 2cm × 2cm to regulate and control sputtering zone
Domain；Then it opens JGP450C type high vacuum dual chamber magnetic control sputtering system general supply and cooling water, three metal targets is put up
Enter sputtering chamber lower part and be separately fixed on bracket, target is that (purity is by Pt (purity 99.9999%), Ru respectively
99.9999%) with Al (purity 99.999%), target position, baffle position and sample position are regulated, be aligned target and sample and is kept off
Plate blocks target and sample, finally closes cavity door, closes exhaust valve.
Sample Room is taken out low vacuum first, air pressure stops after being less than 10Pa；Then by Sample Room pumping high vacuum, vacuum is closed
Meter；Then sputtering chamber is taken out into low vacuum, air pressure stops after being less than 10Pa；Finally by sputtering chamber pumping high vacuum, it is first evacuated to 0.11Pa,
After be evacuated to 0.0005Pa, close vacuum meter, the air pressure of Sample Room and sputtering chamber is in the same order of magnitude and while being not much different can open
Intervening vaive.Start logical argon gas (Ar), stopping when air pressure reaches 2Pa.10W is set by the sputtering power of Pt target and Ru target
To regulate and control the atomic quantity of Pt and Ru, 80W is set by the sputtering power of Al target to regulate and control the atomic quantity of Al；By splashing for three
Penetrating the time is disposed as 1min to control 0.1 μm of ternary alloy three-partalloy of thickness.Shielding power supply is closed after sputtering, closing vacuumizes
Valve opens exhaust valve and deflates, and opens cavity door and takes out sample, obtains PtRuAl-Nafion115 film.After sputtering experiment again
It vacuumizes to protect instrument.
Third step is to prepare corresponding " anode catalyst layer-amberplex ".In embodiment 1, by " PtRuAl-
Nafion115 film " material is put into the sodium hydroxide solution of 2M, and standing obtains " PtRu-Nafion115 film " afterwards for 24 hours.
4th step is to prepare cathode catalysis layer.In embodiment 1, with the graph paper of two suitable areas by 64cm2(8×
8) the commercial electrum (golden atomic molar percentage is 50%) of brilliant white 400nm thickness is clamped, and is cut by the baseline of graph paper
Electrum is then transferred to wet sheet glass using the surface tension of water and is filled by the electrum of 2cm × 2cm out
In the container of ionized water.
65wt%~68wt% nitric acid for analyzing pure rank is put into vessel.The floor space of vessel to facilitate operation for
Preferably, the level suggestion of nitric acid is 3cm.Then vessel are put into 30 DEG C of water-bath, stand a period of time, makes nitric acid
Temperature is constant at 30 DEG C.Needing to cover glass cover during heating prevents from largely volatilizing.Then electrum is turned with sheet glass
It moves on in nitric acid and corrodes 60 minutes.Transfer process not spend the too long of time in case cause between sample etching time difference compared with
Greatly, nitric acid liquid pearl is not fallen on the electrum for floating on liquid level when transfer in order to avoid corroding failure, sample has been put into
Vessel cover is covered after finishing.It takes out sample and being put into deionized water with sheet glass after to the reaction time to clean, at this time brilliant white
Electrum has changed into the porous gold of rufous.It should be noted that the diffusion velocity of nitric acid in water during cleaning
Comparatively fast, it is easy to rush broken porous gold, so needing when being transferred in water porous gold with sheet glass first nitre remaining on sample
Acid drains into deionized water, and then porous gold is put into deionized water again and is cleaned, and stands 20 minutes.So in triplicate,
Substantially nitric acid remaining on sample can be washed.Its transmission electron microscope figure is shown in Fig. 1.
The instrument of platinum plating places schematic diagram and sees Fig. 2.Take the H of 19.3mM2PtCl6Mother liquor, with deionized water by its concentration dilution
To 1.93mM, and it is put into the vessel A of the high 5cm of diameter 10cm wall, the mother liquor amount of taking is advisable with platinum plating solution depth 1cm after diluting,
Then its pH value is adjusted to 9.1 with the sodium hydroxide solution of 1M.The lye measured too much is not used, in the process to avoid mistake
Degree influences the concentration of platinum ion.It covers glass cover and stands 20 minutes.It stands and uses the sodium hydroxide solution of 1M by the PH of plating solution later
Value is accurately adjusted to 9.Porous gold is carefully placed into platinum plating solution at this time.Separately take vessel B, it is proposed that a diameter of 18cm, wall are a height of
9cm.The vessel A for filling platinum plating solution and sample is put into vessel B and in the thermostat water bath for being put into 25 DEG C together that closes the lid
It stands 20~30 minutes so that the platinum ion in plating solution is adequately adsorbed on porous gold and above simultaneously maintains the temperature of reaction system
At 25 DEG C.Finally take the hydrazine hydrate stoste (85wt% of 3ml；Analyze pure) and 3ml deionized water, and uniformly put after being mixed
Enter in vessel B, cover the lid of vessel B and water-bath, is reacted in vessel A using the hydrazine hydrate steam that vessel B is generated.Entirely
Operating process carries out in draught cupboard.It should be noted that hydrazine hydrate has severe toxicity, gas precautions should be carried out so as to avoid an accident.Instead
It is 60 minutes between seasonable.After reaction, the hydrazine hydrate solution in vessel B is outwelled, and vessel A is put into draught cupboard and is pumped
Toxic hydrazine hydrate steam.After completing pumping process, then deionized water is added with conduit into vessel A and facilitates behaviour to promote liquid level
Make while being careful not to rush broken sample thin film.Porous golden Supported Pt Nanoparticles are transferred in deionized water with sheet glass, stand 20~30
Minute.It cleans repeatedly three times to remove wherein remaining plating solution.Porous gold Supported Pt Nanoparticles pass through high resolution transmission electron microscope
It is 0.005 μm that means, which measure its platinum grain size,.Its platinum is tested with EDX8000 energy dispersion type x-ray fluorescence analyzer to support
Amount is 180~220 μ g/cm2.This operation is relatively simple, can realize continuous control by changing reaction time and bath concentration
The loading of platinum processed.
5th step is to prepare corresponding membrane electrode.In embodiment 1, the carbon paper of 100 μ m-thicks is cut into two panels 1cm2
Two panels carbon paper, is then put into the sulfuric acid solution of 2M, 80 by the area of size and supporting layer respectively as anode and cathode
2h is boiled under conditions of DEG C, its hydrophiling is pre-processed.Mass fraction, which is added dropwise, toward the carbon paper back side as cathode support layers later is
0.5% Nafion ethanol solution improves the cohesiveness of cathode support layers carbon paper.Porous golden Supported Pt Nanoparticles are finally directly fished for, it is made
Corrugationless is uniformly laid on cathode support layers carbon paper.
When suppressing membrane electrode, each device places schematic diagram and sees Fig. 3.In embodiment 1, successively by anode support carbon paper
(A), the porous golden Supported Pt Nanoparticles (D) of anode catalyst layer PtRu (B), Nafion115 film (C), cathode catalysis layer, cathode support layers carbon paper
(E) it coincides together and is prepared into membrane electrode.Wherein D is attached on E before preparation, and B is embedded on C, and A need to be placed in by when preparation
The middle part of B and with D close alignment.
In embodiment 1, membrane electrode is prepared with fixture, operation chart is shown in Fig. 3.Fixture is altogether by four part groups
At outermost is that the metal plate of a pair of of 20cm × 20cm plays uniform heat conduction and transmitting pressure, and requires surface absolute
It is smooth；Followed by a pair of 16cm × 16cm polyethers copolymerization acetamide film, which rises, prevents membrane electrode excessively heated；It is thirdly a pair of
The disposable pan paper of 12cm × 12cm and to guarantee absolute cleanliness and without folding line；Most the inside is poly- the four of a pair of of 5cm × 5cm
Fluoride film, and it is common edge on one side that this, which has polytetrafluoroethylene film, and this is carved with 1.1cm to polytetrafluoroethylene film middle
The space of × 1.1cm and be close alignment, two panels polytetrafluoroethylene (PTFE) film thickness is 200 μm, and polytetrafluoroethylene film plays position
The effect of guiding and control compression ratio.A is placed in anode-side polytetrafluoroethylene film at the space 1.1cm × 1.1cm first, it is left
Then BC is put in upper alignment, then fold over cathode side polytetrafluoroethylene film from common edge, finally in cathode side polytetrafluoro
DE, upper left alignment are put in vinyl film at the upper left 1.1cm × 1.1cm.By the compression of polytetrafluoroethylene (PTFE) film gasket control membrane electrode
Than being 20%.Membrane electrode gasket fixture is put into and is careful to operate on hot press, prevents occurring film electricity in the process of moving
The dislocation of pole yin-yang the two poles of the earth.The hot pressing temperature of hot press is preheated to 135 DEG C and is kept, hot pressing pressure is adjusted to 100kg/cm2.It will
Fixture is put on hot press, and hot pressing time is 180 seconds, is taken out fixture after the time and is taken out the membrane electrode prepared.
Porous metals alloy firm in anode assemblies is capable of providing good mass transfer channel, porous metals alloy firm
Ligament both can be used as catalyst, can also be used as conductive daughter, and the thickness range of anode catalyst layer is 0.02~1 μm, than passing
The membrane electrode opposite position of system technique production wants small 2~4 orders of magnitude.Amberplex can provide unobstructed ion transmission
Channel, porous metals alloy firm are embedded in the amberplex of ionic conductivity.The electronics generated in electrochemical reaction can
Carbon paper or carbon cloth by ligament and as anode support are quickly transferred to external circuit, the proton or hydroxide ion of generation
Etc. cathode can be transferred to by the ion transmission channel of amberplex.Porous gold in cathode assembly is also capable of providing good
Mass transfer channel, being attached to the tough platinum taken of porous gold as catalyst has biggish reactivity area.Cathode catalysis layer
Thickness range is 0.02~1 μm, than membrane electrode opposite position also small 2~4 orders of magnitude of traditional handicraft production.Electrochemistry
The electronics generated in reaction can be transferred to from external circuit by carbon paper or carbon cloth as cathode support layers and cathode porous gold
On cathode platinum.Anode catalyst layer and cathode catalysis layer are a kind of macro-scale metal function materials with three-dimensional continuous structure
Material.The performance and working life of the ultra-thin membrane electrode of neat liquid fuel cell of the method preparation are above the film of traditional handicraft production
Electrode.In embodiment 1234, the catalyst usage amount at ultra-thin membrane electrode yin-yang the two poles of the earth be the 50% of traditional handicraft hereinafter, and
Maximum power is near or above the membrane electrode performance of traditional handicraft manufacture.In embodiment 5678, ultra-thin membrane electrode cathode
Catalyst usage amount is the 50% of traditional handicraft hereinafter, and maximum power is more than the membrane electrode performance of traditional handicraft manufacture, explanation
Preparation method provided by the invention can give full play to the performance of material.Yin-yang the two poles of the earth Catalytic Layer thickness range prepared by the present invention
It is 0.02~1 μm, the membrane electrode opposite position than traditional handicraft production is intended to small 2~4 orders of magnitude, membrane electrode after compression
With a thickness of 250~300 μm, with traditional handicraft preparation membrane electrode compared with, using same thickness anode and cathode supporting layer carbon
Under conditions of paper and amberplex, membrane electrode thickness prepared by the present invention is about 60% that traditional handicraft prepares membrane electrode thickness
~65%, improve the volumetric power density of fuel cell.
Embodiment 2-8
For other steps with embodiment 1, difference is " corresponding amberplex to be selected (to be shown in Table 2 the in the first step
5 column)；Corresponding three kinds of metal targets (being shown in Table 1 the 2nd column) are selected in second step；Corresponding corruption is selected in the third step
Erosion time and naoh concentration (being shown in Table 1 the 3rd column)；Corresponding anode-catalyzed layer material and ion is selected to hand in the 5th step
Change film (being shown in Table 2 the 3rd column and the 5th column) ", the performance of obtained material is shown in Table 3, table 4, table 5 and table 6.Embodiment 2-8 membrane electrode yin
The transmission electron microscope figure of pole Catalytic Layer is similar to Fig. 1；The operation chart of cathode catalysis layer preparation is identical as Fig. 2；Film electricity
The structure of pole is similar to Fig. 3, is a difference in that the corresponding anode-catalyzed layer membrane materials of selection and amberplex (are shown in Table 2 the 3rd
Column and the 5th column).
The preparation condition and target material of 1 neat liquid fuel cell membrane electrode anode catalyst layer of table
| Alloy-layer | Remove the reaction condition of Al | Porous metals alloy | |
| Embodiment 1 | PtRuAl | 2M NaOH、24h | PtRu |
| Embodiment 2 | PtSnAl | 2M NaOH、24h | PtSn |
| Embodiment 3 | PtBiAl | 1M NaOH、48h | PtBi |
| Embodiment 4 | PtPbAl | 1M NaOH、48h | PtPb |
| Embodiment 5 | PdCuAl | 1M NaOH、24h | PdCu |
| Embodiment 6 | PdNiAl | 1M NaOH、24h | PdNi |
| Embodiment 7 | AuCuAl | 2M NaOH、48h | AuCu |
| Embodiment 8 | AuPtAl | 2M NaOH、48h | AuPt |
2 neat liquid fuel cell membrane electrode structure of table
Embodiment 9,10
The Catalytic Layer that embodiment 1 and embodiment 2 are obtained, respectively as neat liquid methanol fuel cell membrane electrode anode,
Platinum carrying capacity is 0.2mg/cm2, using porous golden Supported Pt Nanoparticles as neat liquid methanol fuel cell membrane electrode cathode, platinum carrying capacity is
0.2mg/cm2。
Comparative example a is to use Typical spray method, using business PtRu/C as neat liquid methanol fuel cell membrane electrode sun
Pole, platinum carrying capacity are 2mg/cm2.Using Pt/C as neat liquid methanol fuel cell membrane electrode cathode, platinum carrying capacity is 2mg/cm2.Anode
Fuel is the methanol solution of 1M, and flow velocity 4mL/min, cathode oxidant is the hydrogenperoxide steam generator of 20wt%.Pure liquid at 80 DEG C
The maximum power density such as table 3 of body methanol fuel cell electric discharge.
The maximum power density of 3 neat liquid methanol fuel cell of table electric discharge
| 80 DEG C of maximum power densities | |
| Embodiment 9 | 125mW/cm2 |
| Embodiment 10 | 115mW/cm2 |
| Comparative example a | 150mW/cm2 |
From table 3 it can be seen that embodiment 9 and embodiment 10 are used as neat liquid methanol fuel cell membrane electrode anode, it is porous
Golden Supported Pt Nanoparticles are as neat liquid methanol fuel cell membrane electrode cathode.The maximum power density of its 80 DEG C electric discharges is close to comparative example
The maximum power density of a, and the dosage of yin-yang the two poles of the earth platinum is reduced to 10%, illustrates neat liquid methanol fuel provided by the invention
The discharge performance of battery is higher.
Embodiment 11,12
The Catalytic Layer that embodiment 3 and embodiment 4 are obtained, respectively as neat liquid aminic acid fuel battery membrane electrode anode,
Platinum carrying capacity is 0.2mg/cm2, using porous golden Supported Pt Nanoparticles as neat liquid aminic acid fuel battery membrane electrode cathode, Pt carrying capacity is
0.2mg/cm2.Comparative example b is to use Typical spray method, using business Pt/C as neat liquid aminic acid fuel battery membrane electrode sun
Pole, platinum carrying capacity are 2mg/cm2.Using Pt/C as neat liquid aminic acid fuel battery membrane electrode cathode, platinum carrying capacity is 2mg/cm2.Anode
Fuel is the formic acid solution of 1M, and flow velocity 4mL/min, cathode oxidant is the hydrogenperoxide steam generator of 20wt%.Pure liquid at 80 DEG C
The maximum power density such as table 4 of body aminic acid fuel battery electric discharge.
The maximum power density of 4 neat liquid aminic acid fuel battery of table electric discharge
| 80 DEG C of maximum power densities | |
| Embodiment 11 | 135mW/cm2 |
| Embodiment 12 | 126mW/cm2 |
| Comparative example b | 70mW/cm2 |
From table 4, it can be seen that embodiment 11 and embodiment 12 are used as neat liquid aminic acid fuel battery membrane electrode anode, it is porous
Golden Supported Pt Nanoparticles are as neat liquid aminic acid fuel battery membrane electrode cathode.The maximum power density of its 80 DEG C electric discharges is all larger than comparative example
The maximum power density of b, and the carrying capacity of yin-yang the two poles of the earth platinum is reduced to 10%, illustrates neat liquid formic acid fuel provided by the invention
The discharge performance of battery is higher.
Embodiment 13,14
The Catalytic Layer that embodiment 5 and embodiment 6 are obtained, respectively as neat liquid hydrazine hydrate fuel cell membrane electrode sun
Pole, platinum carrying capacity are 0.2mg/cm2, using porous golden Supported Pt Nanoparticles as neat liquid hydrazine hydrate fuel cell membrane electrode cathode, platinum carrying capacity
For 0.2mg/cm2.Comparative example c is to use Typical spray method, using business Pt/C as neat liquid hydrazine hydrate fuel cell membranes electricity
Pole anode, platinum carrying capacity are 0.2mg/cm2.Using Pt/C as neat liquid hydrazine hydrate fuel cell membrane electrode cathode, platinum carrying capacity is
2mg/cm2.Anode fuel is the hydrazine hydrate solution of 10wt%, and flow velocity 6mL/min, cathode oxidant is the peroxidating of 20wt%
Hydrogen solution.The maximum power density of neat liquid hydrazine hydrate fuel cell electric discharge such as table 5 at 80 DEG C.
The maximum power density of 5 neat liquid hydrazine hydrate fuel cell electric discharge of table
| 80 DEG C of maximum power densities | |
| Embodiment 13 | 472mW/cm2 |
| Embodiment 14 | 461mW/cm2 |
| Comparative example c | 204mW/cm2 |
As can be seen from Table 5, embodiment 13 and embodiment 14 are used as neat liquid hydrazine hydrate fuel cell membrane electrode anode, more
Hole gold Supported Pt Nanoparticles are as neat liquid hydrazine hydrate fuel cell membrane electrode cathode.The maximum power densities of its 80 DEG C electric discharges are all larger than pair
The maximum power density of ratio c, and cathode platinum carrying capacity is reduced to 10%, illustrates neat liquid hydrazine hydrate fuel electricity provided by the invention
The discharge performance in pond is higher.
Embodiment 15,16
The Catalytic Layer that embodiment 7 and embodiment 8 are obtained, respectively as neat liquid sodium borohydride fuel cell membrane electrode sun
Pole, platinum carrying capacity are 0.2mg/cm2, using porous golden Supported Pt Nanoparticles as neat liquid sodium borohydride fuel cell membrane electrode cathode, platinum is carried
Amount is 0.2mg/cm2.Comparative example d is to use Typical spray method, using business Pt/C as neat liquid sodium borohydride fuel cell
Membrane electrode anode, platinum carrying capacity are 0.2mg/cm2.Using Pt/C as neat liquid sodium borohydride fuel cell membrane electrode cathode, platinum is carried
Amount is 2mg/cm2.Anode fuel is the sodium borohydride solution of 10wt%, and flow velocity 6mL/min, cathode oxidant is 20wt%'s
Hydrogenperoxide steam generator.The maximum power density such as table 6 that neat liquid sodium borohydride fuel cell discharges at 80 DEG C.
The maximum power density of 6 neat liquid sodium borohydride fuel cell of table electric discharge
| 80 DEG C of maximum power densities | |
| Embodiment 15 | 382mW/cm2 |
| Embodiment 16 | 365mW/cm2 |
| Comparative example d | 180mW/cm2 |
As can be seen from Table 6, embodiment 15 and embodiment 16 are used as neat liquid sodium borohydride fuel cell membrane electrode anode,
Porous gold Supported Pt Nanoparticles are as neat liquid sodium borohydride fuel cell membrane electrode cathode.The maximum power density of its 80 DEG C electric discharges is big
In the maximum power density of comparative example d, and cathode platinum carrying capacity is reduced to 10%, illustrates neat liquid sodium borohydride provided by the invention
The discharge performance of fuel cell is higher.
Unaccomplished matter of the present invention is well-known technique.
Claims (9)
1. a kind of ultra-thin membrane electrode for neat liquid fuel cell, it is characterized in that the composition of the membrane electrode is followed successively by anode-supported
Layer, anode catalyst layer, amberplex, cathode catalysis layer and cathode support layers；
The anode support is identical with cathode support layers, is carbon paper or carbon cloth, with a thickness of 100~200 μm；
The anode catalyst layer is porous metals alloy firm, and with a thickness of 0.02~1 μm, aperture is 0.02~0.1 μm；
The amberplex is cation-exchange membrane or anion-exchange membrane, with a thickness of 25~300 μm；
The cation-exchange membrane is Nafion membrane, and the anion-exchange membrane is AMI film；
The cathode catalysis layer is negative the porous metallic layers of carrying active component, with a thickness of 0.02~1 μm, aperture is 0.02~
0.1μm；Porous metals are gold, and active component is platinum, and load capacity is 180 μ g/cm2~220 μ g/cm2；
The porous metals alloy is the substance obtained after chemical attack removes aluminum metal in the ternary alloy three-partalloy containing aluminium, aperture
It is 0.02~1 μm；The ternary alloy three-partalloy containing Al is selected from the ternary alloy three-partalloy containing PtAl, the ternary alloy three-partalloy containing PdAl, three containing AuAl
One of first alloy；The atomic molar percentage that Al atom accounts for ternary alloy containing Al is 30%~70%.
2. the ultra-thin membrane electrode of neat liquid fuel cell is used for as described in claim 1, it is characterized in that the PtAl ternary
Alloy is PtRuAl, PtSnAl, PtBiAl or PtPbAl；The ternary alloy three-partalloy containing PdAl is PdCuAl or PdNiAl；Institute
The ternary alloy three-partalloy containing AuAl stated is AuCuAl or AuPtAl.
3. the ultra-thin membrane electrode of neat liquid fuel cell is used for as described in claim 1, it is characterized in that the porous metals
For porous gold will be obtained after component removal active metal active in the bianry alloy for containing gold.
4. the ultra-thin membrane electrode of neat liquid fuel cell is used for as claimed in claim 3, it is characterized in that two containing Au
First alloy is specially electrum, and golden atomic molar percentage is 40%~60%.
5. the preparation method for the ultra-thin membrane electrode of neat liquid fuel cell as described in claim 1, it is characterized in that including
Following steps:
(1) amberplex is sequentially placed into hydrogenperoxide steam generator and dilution heat of sulfuric acid under conditions of 60 DEG C~100 DEG C, respectively
Boil 0.5h~1.5h；The amberplex with a thickness of 25 μm~300 μm；
(2) in high vacuum dual chamber magnetic control sputtering system, ternary alloy three-partalloy is sputtered in the ion exchange film surface that upper step obtains, when
Between be 1min~3min；The ternary alloy three-partalloy of sputtering with a thickness of 0.02~1 μm；
(3) " ternary alloy three-partalloy-amberplex " material that upper step obtains is put into the NaOH lye of 1M~3M corrode for 24 hours~
48h obtains corresponding anode catalyst layer and ion exchange membrane material；
(4) by the electrum of 0.02~1 μ m-thick the nitric acid of 65wt%~68wt%, 20 DEG C~40 DEG C at a temperature of corrode
40min~80min is to obtain porous gold；Separately with lye by the pH value adjustment of 1mM~2mM platinum acid chloride solution to 9~10, and will be anti-
It answers the temperature of system to maintain 20 DEG C~30 DEG C, then obtained porous gold is put into platinum acid chloride solution, is produced with hydrazine solution
Platinum ion of the raw hydrazine steam reduction adsorption on porous gold, reaction 30min~90min obtain the porous gold load of film-form
Platinum needs to fish for porous golden Supported Pt Nanoparticles with cathode carbon paper after the completion of preparation；
The platinum content supported on the porous gold is 180 μ g/cm2~220 μ g/cm2；The volume ratio of hydrazine solution by " hydrazine hydrate:
Water=1~2:1 " is obtained by mixing；
(5) hot pressing temperature of hot press and hot pressing pressure are adjusted to 120 DEG C~150 DEG C and 80kg/cm respectively first2~120
kg/cm2, then use fixture from anode to cathode successively by " anode carbon paper, anode catalyst layer, amberplex, cathode catalysis layer
With cathode carbon paper " alignment is clipped together, and be put on hot press, finally controlling hot pressing time is 120~240s；Obtain ultrathin membrane
Electrode.
6. the preparation method for the ultra-thin membrane electrode of neat liquid fuel cell as claimed in claim 5, it is characterized in that described
The step of (1) in hydrogenperoxide steam generator concentration range be 3wt%~5wt%；The dilute sulfuric acid concentration is 0.5M~1M.
7. the preparation method for the ultra-thin membrane electrode of neat liquid fuel cell as claimed in claim 5, it is characterized in that described
Ultra-thin membrane electrode with a thickness of 250 μm~300 μm.
8. the preparation method for the ultra-thin membrane electrode of neat liquid fuel cell as claimed in claim 5, it is characterized in that described
The ultra-thin membrane electrode for neat liquid fuel cell application, be used for neat liquid fuel cell.
9. the preparation method for the ultra-thin membrane electrode of neat liquid fuel cell as claimed in claim 8, it is characterized in that described
Neat liquid fuel cell be specially hydrazine hydrate-hydrogen peroxide as fuel battery, sodium borohydride-hydrogen peroxide as fuel battery, methanol-dioxygen
Water fuel cell or formic acid-hydrogen peroxide fuel cell.
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| CN111926344A (en) * | 2020-08-01 | 2020-11-13 | 中国空间技术研究院 | Photosynthetic reaction device and method for manufacturing membrane electrode |
| CN114583194A (en) * | 2022-03-01 | 2022-06-03 | 天津理工大学 | Large porosity catalyst layer suitable for proton exchange membrane fuel cell |
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