CN103887531B - A kind of ordering gas-diffusion electrode and preparation thereof and application - Google Patents

A kind of ordering gas-diffusion electrode and preparation thereof and application Download PDF

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CN103887531B
CN103887531B CN201210563166.5A CN201210563166A CN103887531B CN 103887531 B CN103887531 B CN 103887531B CN 201210563166 A CN201210563166 A CN 201210563166A CN 103887531 B CN103887531 B CN 103887531B
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ordering
gas
electrode
pdda
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CN103887531A (en
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孙公权
夏章讯
王素力
姜鲁华
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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

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Abstract

The present invention relates to a kind of ordering gas-diffusion electrode and preparation thereof and application, described membrane electrode is made up of gas diffusion layers and Catalytic Layer, described Catalytic Layer is ordering Catalytic Layer, and it is due to the conductive polymer nanometer line of gas diffusion layers surface ordering array arrangement and is doped in the PDDA (PDDA) on conductive polymer nanometer line surface and interacts with Pt catalyst particle and form.Ordering membrane electrode of the present invention has precious metals pt utilization rate height, stability advantages of higher, can effectively reduce fuel-cell catalyst cost, improves fuel battery service life；Meanwhile, membrane electrode of the present invention can effectively strengthen fuel mass transfer in Catalytic Layer, thus improves the utilization rate of fuel；Ordering membrane electrode of the present invention can be as Proton Exchange Membrane Fuel Cells, direct liquid fuel battery and PEM water type electrolyzer membrane electrode.

Description

A kind of ordering gas-diffusion electrode and preparation thereof and application
Technical field
The present invention relates to ordering gas-diffusion electrode and preparation thereof and application, a kind of can be used for Proton Exchange Membrane Fuel Cells, direct liquid fuel battery or the gas-diffusion electrode of proton exchange model water electrolytic cell.The invention still further relates to the preparation method of above-mentioned ordering gas-diffusion electrode.
Background technology
Proton Exchange Membrane Fuel Cells, due to features such as its efficient, environmental friendliness, is paid close attention to by research institution of various countries in recent years.Membrane electrode (MEA), as the core component of fuel cell, is generally made up of gas diffusion layers, Catalytic Layer and PEM.Catalytic Layer is that the place of electrochemical reaction occurs in membrane electrode assembly (MEA), and the performance of Catalytic Layer and stability determine the chemical property of MEA largely, and the cost of the eelctro-catalyst in Catalytic Layer also account for the significant proportion of MEA totle drilling cost simultaneously.In order to improve performance and the stability of Catalytic Layer, reducing wherein eelctro-catalyst consumption, it is a kind of new method that design preparation possesses the MEA of microstructure ordering Catalytic Layer.At present, in conventional MEA, the preparation method of Catalytic Layer is: eelctro-catalyst is dispersed in ethanol, in ethylene glycol equal solvent, adds appropriateAs binding agent, the uniform catalyst slurry of fully dispersed formation.The methods such as this catalyst slurry passes through spraying, brushing are prepared on diffusion layer formation GDE formation gases diffusion electrode, or are prepared on PEM the membrane electrode forming CCM structure.In above-mentioned traditional gas-diffusion electrode or membrane electrode, catalyst granules existsForming loose porous thin layer under binding agent effect, reactant resistance to mass tranfer in unordered duct is relatively big, affects battery combination property.
In sum, the MEA with nano orderedization structured catalyst layers is manufactured most important for reducing Proton Exchange Membrane Fuel Cells cost and raising proton exchange film fuel battery performance.
Catalytic Layer is prepared in Pt-PDDA self assembly, it it is the positive charge group utilizing PDDA, with electronegative containing Pt ion, such as chloroplatinic acid radical ion, by the electrostatic interaction of positive and negative charge, the self assembling process carried out, then prepares the Pt nanoparticle of high degree of dispersion by electronation, to improve the dispersion that Pt supports thus the utilization rate improving Pt.In document, the method for report, is typically employed in unordered carbon support and directly carries out self assembly, and Catalytic Layer stability under high potential and material transmission performance are the best.
Summary of the invention
It is an object of the invention to provide a kind of novel ordering gas-diffusion electrode, this gas-diffusion electrode has the advantages such as Pt catalyst stability is high, effective rate of utilization is high, Catalytic Layer mass-transfer performance is good, can be used as in Proton Exchange Membrane Fuel Cells, direct liquid fuel battery or proton exchange model water electrolytic cell.
For achieving the above object, the present invention uses scheme in detail below to realize:
A kind of ordering gas-diffusion electrode, including gas diffusion layers and ordering Catalytic Layer based on gas diffusion layers, ordering Catalytic Layer is attached to gas diffusion layers surface, and has the nanowire array structure of the ordered orientation being perpendicular in gas diffusion layers surface direction on microcosmic.
Described ordering Catalytic Layer includes conductive polymer nanometer line a kind of in the polythiophene of array arrangement on microcosmic or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or polyaniline derivative, and it is attached to the PDDA on conductive polymer nanometer line, and the Pt nanoparticle being connected with PDDA；
In ordering Catalytic Layer, the loading of conductive polymer nanometer line is 0.5mgcm-2, the loading of PDDA is 5 μ gcm-2, the loading of Pt nanoparticle is 0.01-0.5mgcm-2。
Described gas diffusion layers is by supporting layer and is attached to the microporous layers of supporting layer one side surface and forms；Described supporting layer is carbon paper or carbon cloth；Described microporous layers be after VulcanXC-72 carbon dust, acetylene black carbon dust, CNT or Graphene mixing PTFE or Nafion by blade coating, brush or be sprayed into support layer surface and prepare.
The preparation method of described ordering gas-diffusion electrode, including following preparation process,
A.PDDA(PDDA) preparation of ordering nanowire array structure adulterated
Use the method for the electro-deposition one in the microporous layers surface doping of gas diffusion layers one side surface or gas diffusion layers has the conducting polymer polythiophene of PDDA or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or polyaniline derivative, obtain being perpendicular on microcosmic the conductive polymer nanometer linear array structure of the PDDA doping of the ordered orientation in diffusion layer surface direction；
B. prepared by the self assembly of Catalytic Layer
It is 1-10mgmL by Pt concentration-1Chloroplatinic acid aqueous solution with every square centimeter of 10-100 μ L drop coating in above-mentioned steps a gained nanowire array structure surface, left at room temperature 12-24 hour；By the amount Vitamin C aqueous acid of 2-10 times of Pt material or the aqueous solution of sodium borohydride or the aqueous solution of Dimethyl Ammonium borine or hydrazine hydrate drop coating in above-mentioned conductive polymer nanometer linear array surface, stand 2-10 hour, it is dried under room temperature after deionized water rinsing, obtains ordering gas-diffusion electrode.
Electro-deposition method in described step a particularly as follows: gas diffusion layers side be impregnated in containing a kind of in thiophene or pyrroles or aniline or thiophene derivant or azole derivatives or anil solution, contain in the electrolyte of supporting electrolyte and PDDA simultaneously, using gas diffusion layers as working electrode, Pt sheet is as to electrode, saturated calomel electrode, as reference electrode, uses three-electrode system to carry out electro-deposition.
In step a, when the molecular weight of described PDDA is less than 100,000, the mass concentration of PDDA aqueous solution is 20-30%；When the molecular weight of described PDDA is more than or equal to 100,000 less than 200,000, the concentration of PDDA aqueous solution is more than 30%, and less than or equal to 50%；
In step b, the concentration of described chloroplatinic acid aqueous solution is 1-10mg ml-1。
In described electrodeposition process electrolyte solution, the concentration of thiophene or pyrroles or aniline or thiophene derivant or azole derivatives or anil is 0.01-0.5M；
The supporting electrolyte added in described electrodeposition process electrolyte solution is one or more in paratoluenesulfonic acid sodium salt, dodecyl sodium sulfate, beta-naphthalenesulfonic-acid, the silica-based trifluoroacetamide of double trimethyl, perchlorate, sulfate, chloride；In described electrodeposition process electrolyte solution, the concentration of supporting electrolyte is 0.01-0.5M；
Its electro-deposition current potential of described electro-deposition is 0.75-1.1V(vsNHE)；
The a length of 0.25-1h of its electrodeposition time of described electro-deposition.
In described electrolyte, the mass concentration of PDDA is 0.05-5%.
Described ordering gas-diffusion electrode can be used in Proton Exchange Membrane Fuel Cells or direct liquid fuel battery or proton exchange model water electrolytic cell.
Compared with prior art, the invention have the advantages that
1. catalyst stability is high: gas-diffusion electrode of the present invention (includes gas-diffusion electrode and the membrane electrode of CCM structure of GDE structure with the membrane electrode using traditional handicraft to prepare, lower with) compared with, because Pt catalyst nanoparticles is attached on the conducting polymer of oldered array arrangement, there is the advantage that catalyst stability is high；
2. catalyst utilization is high: using ordering gas-diffusion electrode prepared by the method for the invention compared to conventional film electrode, increase catalyst effectively utilizes area, improves the unit mass oxygen reducing ability of catalyst；
3. in Catalytic Layer, mass-transfer performance is good: use ordering gas-diffusion electrode of the present invention, and owing to its Catalytic Layer is ordering array arrangement, compared to the Catalytic Layer of traditional unordered arrangement, fuel or the oxidant mass-transfer performance in Catalytic Layer is more excellent；
The most practical: compared to using the substrate grown ordered nano-structures such as other such as silicon, gold, quartz, this method uses gas diffusion layers simple as the growth substrate method of conductive polymers ordered nano structure, without strip step such as follow-up hot pressing, do not destroy the integrity of structure, and conducting polymer is better than material with carbon element in the stability of high potential, the catalyst caused due to carbon corrosion will not be occurred to assemble.
Accompanying drawing explanation
Fig. 1 (a) of the present invention ordering gas-diffusion electrode, (b) traditional gas diffusion electrode structure schematic diagram.It can be seen that compared with traditional gas diffusion electrode (b), the loading of 1. ordering gas-diffusion electrode (a) Pt catalyst is relatively low；2. in ordering gas-diffusion electrode (a), Pt is combined with the PDDA being positioned at ordering conductive polymer surfaces by electrostatic interaction, achieve the supporting of polymolecularity of Pt nanoparticle, improve catalyst loading and be exposed to the catalyst ratio that surface can effectively utilize；3. the array arrangement formed in ordering gas-diffusion electrode (a) is conducive to reactant and product at the mass transfer of Catalytic Layer, is conducive to improving the utilization rate of reactant, thus improves battery performance.
Fig. 2 is a kind of uses the method for the invention electromicroscopic photograph (embodiment 1) after diffusion layer surface electro-deposition conducting polymer PPy；Can be seen that PPy nano wire presents the oldered array structure being perpendicular to surface on the microporous layers surface of gas diffusion layers, improve Pt particle and effectively support area, and provide the passage carrying out active substance transmission.
Fig. 3 is a kind of use that the method for the invention prepares catalyst-loaded after the electromicroscopic photograph (embodiment 1) of ordering gas-diffusion electrode；It can be seen that Pt nanoparticle is uniformly distributed on PPy surface, present the Particle Cluster of reunion in the site that there is PDDA so that Pt particle is effectively exposed to three-phase reaction interface, improve the utilization rate of Pt particle.
Fig. 4 is the cyclic voltammetry curve of commodity E-Tek catalyst (b) in embodiment 1 in ordering membrane electrode catalyst (a) and comparative example 1, and electrolyte solution is N2Saturated 0.5M sulfuric acid solution, sweeping the rate of hastening is 50mV s-1.Can be seen that from the result of calculation of this figure, in embodiment 1, the electrochemical active surface of ordering membrane electrode catalytic layer is up to 55.4 square metres of every gram of platinum, improve 40% compared to 39.6 square metres of every gram of platinum of the electrochemical active surface of commercial catalyst in comparative example 1, catalyst utilization is greatly improved.
Cyclic voltammetry curve before and after traditional gas diffusion electrode commodity E-Tek catalyst (b) burn-in test in ordering gas-diffusion electrode catalyst (a) and comparative example 1 in Fig. 5 embodiment 1, Fig. 5 (c) is the normalized electrochemical surface area of catalyst in Catalytic Layer before and after burn-in test；Wherein electrolyte solution is 0.5M sulfuric acid solution saturated for N2, and sweep limits is 0.85-1.2Vvs.NHE, and sweep speed is 200mV s-1, the scanning number of turns is 1000 circles.As can be seen from the figure, scanning through 1000 circles, before the electrochemical active surface of catalyst can be maintained at burn-in test in ordering gas-diffusion electrode Catalytic Layer more than 60%, and about 40% before the electrochemical active surface of E-Tek catalyst is down to burn-in test in traditional gas diffusion electrode Catalytic Layer, this is conducting polymer mainly due to the catalyst carrier in ordering gas-diffusion electrode, and conducting polymer is the most perishable under high potential, therefore, its stability is compared to the good stability of carbon supported catalyst in traditional gas diffusion electrode, i.e. illustrate that this ordering gas diffusion electrode structures is for keeping the stability of catalyst to serve important function.
Hydrogen reduction test curve before and after traditional gas diffusion electrode commodity E-Tek catalyst (b) burn-in test in ordering gas-diffusion electrode catalyst (a) and comparative example 1 in Fig. 6 embodiment 1, wherein electrolyte solution is O2Saturated 0.5M sulfuric acid solution, sweep speed is 20mV s-1.As can be seen from the figure, scanning through 1000 circles, catalyst oxygen reduction half wave potential in ordering gas-diffusion electrode Catalytic Layer declines about 8mV, and the hydrogen reduction half wave potential of E-Tek catalyst declines more than 20mV in traditional gas diffusion electrode Catalytic Layer, this is conducting polymer mainly due to the catalyst carrier in ordering gas-diffusion electrode, and conducting polymer is the most perishable under high potential, therefore its stability is compared to the good stability of carbon supported catalyst in traditional gas diffusion electrode, i.e. illustrate that in this ordering gas-diffusion electrode, structure is for keeping the catalytic oxidation-reduction stability of catalyst to serve important function.
Detailed description of the invention
Below by way of example, the present invention is described in detail, but the present invention is not limited only to following example.
Embodiment 1:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
2) preparation of ordering gas-diffusion electrode:
A. the preparation of the ordering nanowire array structure that surface is modified
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and insertion one conduction platinized platinum in plastic clamp, ensures that conduction platinized platinum contacts well with gas diffusion layers simultaneously.Said apparatus is placed in three electrode electro-deposition systems, contacting good conduction platinized platinum with gas diffusion layers is working electrode, saturated calomel electrode is to electrode and reference electrode, electrolyte is containing 0.1M pyrroles, 0.1M paratoluenesulfonic acid sodium salt, mass concentration is the Ultra-low molecular weight (MW < 100 of 1%, 000) the 0.2M phosphate buffer of PDDA, running voltage 0.65V(vsSCE is applied) on conduction platinized platinum, persistent period 30min, the polypyrrole (PPy) of the doping PDDA of one layer of ordering array arrangement is i.e. formed in the electro-deposition of gas diffusion layers surface, it is labeled as PDDAPPy-GDL sample.
B. prepared by the self assembly of Catalytic Layer
Pt amount will be contained for 7.4mgmL-1Chloroplatinic acid aqueous solution by every square centimeter of 20 μ L drop coatings in above-mentioned steps 2) conductive polymer surfaces of a gained PDDAPPy-GDL sample, stand 24 hours.It is 37mgmL by concentration-1Aqueous ascorbic acid also according to every square centimeter of 20 μ L drop coatings in the conductive polymer surfaces of the above-mentioned PDDAPPy-GDL sample being spotted with chloroplatinic acid, stand 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the conductive polymer surfaces of the PDDAPPy-GDL sample having supported catalyst with deionized water, after air-drying ordering gas-diffusion electrode.
Embodiment 2:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
The dilute powder ultrasonic of graphite prepared by dilatometry is scattered in ethanol solution, supports serosity in above-mentioned gas diffusion layer microporous layers surface with knife coating, weighs, until carrying capacity is 0.2mgcm-2.Obtain the gas diffusion layers of the dilute modification of graphite.
2) preparation of ordering gas-diffusion electrode:
A. the preparation of the ordering nanowire array structure that surface is modified
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and insertion one conduction platinized platinum in plastic clamp, ensures conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in three electrode electro-deposition systems, electrolyte is containing the Ultra-low molecular weight (MW < 100 that 0.1M pyrroles, 0.1M paratoluenesulfonic acid sodium salt, mass concentration are 1%, 000) the 0.2M phosphate buffer of PDDA, running voltage 0.65V(vsSCE is applied) on conduction platinized platinum, persistent period 30min, i.e. form the polypyrrole (PPy) of the doping PDDA of one layer of ordering array arrangement in the electro-deposition of gas diffusion layers surface, be labeled as PDDAPPy-GDL sample.
B. prepared by the self assembly of Catalytic Layer
Pt amount will be contained for 7.4mgmL-1Chloroplatinic acid aqueous solution by every square centimeter of 20 μ L drop coatings in above-mentioned steps 2) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, stands 24 hours.It is 37mgmL by concentration-1Aqueous ascorbic acid also according to every square centimeter of 20 μ L drop coatings in the above-mentioned electrode surface being spotted with chloroplatinic acid, stand 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface having supported catalyst with deionized water, after air-drying ordering membrane electrode.
Embodiment 3:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
Multi-walled carbon nano-tubes powder ultrasonic chemical meteorology deposition method prepared is scattered in ethanol solution, supports serosity in above-mentioned gas diffusion layer microporous layers surface with knife coating, weighs, until carrying capacity is 0.2mgcm-2.Obtain carbon nano tube modified gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure that surface is modified
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and insertion one conduction platinized platinum in plastic clamp, ensures conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in three electrode electro-deposition systems, electrolyte is containing the Ultra-low molecular weight (MW < 100 that 0.1M pyrroles, 0.1M paratoluenesulfonic acid sodium salt, mass concentration are 1%, 000) the 0.2M phosphate buffer of PDDA, running voltage 0.65V(vsSCE is applied) on conduction platinized platinum, persistent period 30min, i.e. form the polypyrrole (PPy) of the doping PDDA of one layer of ordering array arrangement in the electro-deposition of gas diffusion layers surface, be labeled as PDDAPPy-GDL sample.
B. prepared by the self assembly of Catalytic Layer
Pt amount will be contained for 7.4mgmL-1Chloroplatinic acid aqueous solution by every square centimeter of 20 μ L drop coatings in above-mentioned steps 2) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, stands 24 hours.It is 37mgmL by concentration-1Aqueous ascorbic acid also according to every square centimeter of 20 μ L drop coatings in the above-mentioned electrode surface being spotted with chloroplatinic acid, stand 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface having supported catalyst with deionized water, after air-drying ordering membrane electrode.
Embodiment 4:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure that surface is modified
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and insertion one conduction platinized platinum in plastic clamp, ensures conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in three electrode electro-deposition systems, electrolyte is containing the Ultra-low molecular weight (MW < 100 that 0.1M pyrroles, 0.1M paratoluenesulfonic acid sodium salt, mass concentration are 1%, 000) the 0.2M phosphate buffer of PDDA, running voltage 0.75V(vsSCE is applied) on conduction platinized platinum, persistent period 60min, i.e. form the polypyrrole (PPy) of the doping PDDA of one layer of ordering array arrangement in the electro-deposition of gas diffusion layers surface, be labeled as PDDAPPy-GDL sample.
B. prepared by the self assembly of Catalytic Layer
Pt amount will be contained for 7.4mgmL-1Chloroplatinic acid aqueous solution by every square centimeter of 40 μ L drop coatings in above-mentioned steps 2) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, stands 24 hours.It is 37mgmL by concentration-1Aqueous ascorbic acid also according to every square centimeter of 40 μ L drop coatings in the above-mentioned electrode surface being spotted with chloroplatinic acid, stand 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface having supported catalyst with deionized water, after air-drying ordering membrane electrode.
Embodiment 5:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure that surface is modified
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and insertion one conduction platinized platinum in plastic clamp, ensures conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in three electrode electro-deposition systems, electrolyte is containing the Ultra-low molecular weight (MW < 100 that 0.1M pyrroles, 0.1M paratoluenesulfonic acid sodium salt, mass concentration are 1%, 000) the 0.2M phosphate buffer of PDDA, running voltage 0.6V(vsSCE is applied) on conduction platinized platinum, persistent period 20min, i.e. form the polypyrrole (PPy) of the doping PDDA of one layer of ordering array arrangement in the electro-deposition of gas diffusion layers surface, be labeled as PDDAPPy-GDL sample.
B. prepared by the self assembly of Catalytic Layer
Pt amount will be contained for 7.4mgmL-1Chloroplatinic acid aqueous solution by every square centimeter of 10 μ L drop coatings in above-mentioned steps 2) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, stands 24 hours.It is 37mgmL by concentration-1Aqueous ascorbic acid also according to every square centimeter of 10 μ L drop coatings in the above-mentioned electrode surface being spotted with chloroplatinic acid, stand 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface having supported catalyst with deionized water, after air-drying ordering membrane electrode.
Embodiment 6:
1) preparation of gas diffusion layers:
SGL carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure that surface is modified
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and insertion one conduction platinized platinum in plastic clamp, ensures conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in three electrode electro-deposition systems, electrolyte is containing the Ultra-low molecular weight (MW < 100 that 0.1M pyrroles, 0.1M paratoluenesulfonic acid sodium salt, mass concentration are 1%, 000) the 0.2M phosphate buffer of PDDA, running voltage 0.65V(vsSCE is applied) on conduction platinized platinum, persistent period 30min, i.e. form the polypyrrole (PPy) of the doping PDDA of one layer of ordering array arrangement in the electro-deposition of gas diffusion layers surface, be labeled as PDDAPPy-GDL sample.
B. prepared by the self assembly of Catalytic Layer
Pt amount will be contained for 7.4mgmL-1Chloroplatinic acid aqueous solution by every square centimeter of 20 μ L drop coatings in above-mentioned steps 2) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, stands 24 hours.It is 37mgmL by concentration-1Aqueous ascorbic acid also according to every square centimeter of 20 μ L drop coatings in the above-mentioned electrode surface being spotted with chloroplatinic acid, stand 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface having supported catalyst with deionized water, after air-drying ordering membrane electrode.
Comparative example 1:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
2) preparation of catalyst slurry:
3mg commodity platinum C catalyst (E-Tek) is placed in beaker, adds 50mg deionized water, ultrasonic disperse 5 minutes.Add the Nafion solution (DuPont) of 7mg5%, ultrasonic disperse 5 minutes.Add 50mg dehydrated alcohol, ultrasonic disperse 30 minutes, obtain catalyst slurry.
3) preparation of Catalytic Layer:
By above-mentioned steps 1) gained sample is fixed in vacuum thermal station, is heated to 60 DEG C, takes off and weigh, retighten in thermal station after 30 minutes；Take above-mentioned by step 2) gained catalyst slurry with nitrogen airbrush even application in step 1) gained sample surfaces, spraying terminate after, at 60 DEG C keep 30 minutes, take off and weigh, catalyst loading is about 0.5mg cm-2.Obtain traditional structure membrane electrode.
Comparative example 2:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully takes out after infiltration and air-dry, weigh.Above-mentioned steps is repeated, until PTFE carrying capacity is carbon paper quality after the process of 15%(hydrophobization) left and right.By VulcanXC-72 carbon dust with relative to carbon dust and PTFE mass and 10% mass concentration 20%PTFE aqueous solution uniform, after the ethanol dilution with 20 times of carbon dust quality, under ultrasound condition, dispersion 20 minutes, stir.The carbon paper that above-mentioned hydrophobization processes is placed on glass plate fixing, above-mentioned serosity is scratched in carbon paper surface, weighs, until carbon dust carrying capacity is 1mgcm-2, i.e. obtain gas diffusion layers.
2) preparation of catalyst slurry:
3mg commodity platinum black catalyst (JM) is placed in beaker, adds 50mg deionized water, ultrasonic disperse 5 minutes.Add the Nafion solution (DuPont) of 7mg5%, ultrasonic disperse 5 minutes.Add 50mg dehydrated alcohol, ultrasonic disperse 30 minutes, obtain catalyst slurry.
3) preparation of Catalytic Layer:
By above-mentioned steps 1) gained sample is fixed in vacuum thermal station, is heated to 60 DEG C, takes off and weigh, retighten in thermal station after 30 minutes；Take above-mentioned by step 2) gained catalyst slurry with nitrogen airbrush even application in step 1) gained sample surfaces, spraying terminate after, at 60 DEG C keep 30 minutes, take off and weigh, catalyst loading is about 0.5mg cm-2.Obtain traditional structure membrane electrode.

Claims (8)

1. the preparation method of an ordering gas-diffusion electrode, it is characterised in that: include following preparation process,
The preparation of the ordering nanowire array structure of a.PDDA polydiene base the third alkyl dimethyl ammonium chloride doping
The method using electro-deposition has the conducting polymer of PDDA at the microporous layers surface doping of gas diffusion layers one side surface or gas diffusion layers, described conducting polymer is the one in polythiophene or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or polyaniline derivative, obtains being perpendicular on microcosmic the conductive polymer nanometer linear array structure of the PDDA doping of the ordered orientation in diffusion layer surface direction；
B. prepared by the self assembly of Catalytic Layer
It is 1-10mg mL by Pt concentration-1Chloroplatinic acid aqueous solution with every square centimeter of 10-100 μ L drop coating in above-mentioned steps a gained nanowire array structure surface, left at room temperature 12-24 hour；By one or more drop coatings in Vitamin C aqueous acid or the aqueous solution of sodium borohydride or the aqueous solution of Dimethyl Ammonium borine or hydrazine hydrate in above-mentioned conductive polymer nanometer linear array surface, make 2-10 times of the amount that amount is Pt material of the material of ascorbic acid or sodium borohydride or Dimethyl Ammonium borine or hydrazine hydrate, stand 2-10 hour, it is dried under room temperature after deionized water rinsing, obtains ordering gas-diffusion electrode；
Use ordering gas-diffusion electrode prepared by described method, including gas diffusion layers and ordering Catalytic Layer based on gas diffusion layers, ordering Catalytic Layer is attached to gas diffusion layers surface, and has the nanowire array structure of the ordered orientation being perpendicular in gas diffusion layers surface direction on microcosmic.
2. the preparation method of ordering gas-diffusion electrode as claimed in claim 1, it is characterised in that:
Electro-deposition method in described step a particularly as follows: gas diffusion layers side be impregnated in containing a kind of in thiophene or pyrroles or aniline or thiophene derivant or azole derivatives or anil solution, contain in the electrolyte of supporting electrolyte and PDDA simultaneously, using gas diffusion layers as working electrode, Pt sheet is as to electrode, saturated calomel electrode, as reference electrode, uses three-electrode system to carry out electro-deposition.
3. the preparation method of ordering gas-diffusion electrode as claimed in claim 1, it is characterised in that:
In step a, when the molecular weight of described PDDA is less than 100,000, the mass concentration of PDDA aqueous solution is 20-30%；When the molecular weight of described PDDA is more than or equal to 100,000 less than 200,000, the mass concentration of PDDA aqueous solution is more than 30%, and less than or equal to 50%；
In step b, the concentration of described chloroplatinic acid aqueous solution is 1-10mg ml-1。
4. the preparation method of ordering gas-diffusion electrode as claimed in claim 1 or 2, it is characterised in that:
In described electrodeposition process electrolyte solution, the concentration of thiophene or pyrroles or aniline or thiophene derivant or azole derivatives or anil is 0.01-0.5M；
The supporting electrolyte added in described electrodeposition process electrolyte solution is one or more in paratoluenesulfonic acid sodium salt, dodecyl sodium sulfate, beta-naphthalenesulfonic-acid, the silica-based trifluoroacetamide of double trimethyl, perchlorate, sulfate, chloride；In described electrodeposition process electrolyte solution, the concentration of supporting electrolyte is 0.01-0.5M；
Its electro-deposition current potential of described electro-deposition is 0.65-0.75V relative to saturated calomel electrode；
The a length of 0.25-1h of its electrodeposition time of described electro-deposition.
5. the preparation method of ordering gas-diffusion electrode as claimed in claim 2, it is characterised in that:
In described electrolyte, the mass concentration of PDDA is 0.05-5%.
6. the preparation method of ordering gas-diffusion electrode as claimed in claim 1, it is characterised in that:
Described ordering Catalytic Layer includes conductive polymer nanometer line a kind of in the polythiophene of array arrangement on microcosmic or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or polyaniline derivative, and it is attached to the PDDA on conductive polymer nanometer line, and the Pt nanoparticle being connected with PDDA；
In ordering Catalytic Layer, the loading of conductive polymer nanometer line is 0.5mg cm-2, the loading of PDDA is 5 μ g cm-2, the loading of Pt nanoparticle is 0.01-0.5mg cm-2。
7. the preparation method of ordering gas-diffusion electrode as claimed in claim 1, it is characterised in that:
Described gas diffusion layers is by supporting layer and is attached to the microporous layers of supporting layer one side surface and forms；
Described supporting layer is carbon paper or carbon cloth；Described microporous layers be after VulcanXC-72 carbon dust, acetylene black carbon dust, CNT or Graphene mixing PTFE or Nafion by blade coating, brush or be sprayed into support layer surface and prepare.
8. the preparation method of ordering gas-diffusion electrode as claimed in claim 1, it is characterised in that:
Ordering gas-diffusion electrode prepared by described method is in Proton Exchange Membrane Fuel Cells or direct liquid fuel battery or proton exchange model water electrolytic cell.
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