CN103887531A - Ordered gas diffusion electrode and preparation and application thereof - Google Patents

Ordered gas diffusion electrode and preparation and application thereof Download PDF

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CN103887531A
CN103887531A CN201210563166.5A CN201210563166A CN103887531A CN 103887531 A CN103887531 A CN 103887531A CN 201210563166 A CN201210563166 A CN 201210563166A CN 103887531 A CN103887531 A CN 103887531A
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ordering
electrode
gas
pdda
gas diffusion
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CN103887531B (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

Abstract

The invention relates to an ordered gas diffusion electrode, preparation and application thereof. The membrane electrode comprises a gas diffusion layer and a catalysis layer; the catalysis layer is an ordered catalysis layer, and is formed by interaction of conductive polymer nanowires arranged in an ordered array manner on the gas diffusion layer surface and phthalic acid diethylene glycol diacrylate (PDDA) doped on the surface of the conductive polymer nanowires with Pt catalyst particles. The ordered membrane electrode of the invention has the advantages of high utilization rate of precious metal Pt, high stability, and the like, can effectively reduces catalyst cost of fuel cells, and can improve the service life of fuel cells; meanwhile, the membrane electrode of the invention can effectively enhance the mass transfer of fuel in the catalysis layer, thereby improving the fuel utilization rate; the ordered membrane electrode of the invention can be used as a membrane electrode of proton exchange membrane fuel cells, direct liquid fuel cells, and proton exchange membrane water-type electrolytic baths.

Description

A kind of ordering gas-diffusion electrode and preparation and application
Technical field
The present invention relates to ordering gas-diffusion electrode and preparation thereof and application, specifically a kind of gas-diffusion electrode that can be used for Proton Exchange Membrane Fuel Cells, direct liquid fuel battery or 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 it is efficient, environmental friendliness, is subject to the close attention of research institution of various countries in recent years.Membrane electrode (MEA), as the core component of fuel cell, is made up of gas diffusion layers, Catalytic Layer and proton exchange membrane conventionally.Catalytic Layer is the place that electrochemical reaction occurs in membrane electrode assembly (MEA), and the performance of Catalytic Layer and stability have determined the chemical property of MEA largely, and the cost of the eelctro-catalyst in Catalytic Layer has also accounted for the significant proportion of MEA total cost simultaneously.In order to improve performance and the stability of Catalytic Layer, reduce wherein eelctro-catalyst consumption, the MEA that design preparation possesses microstructure ordering Catalytic Layer is a kind of new method.At present, in conventional MEA, the preparation method of Catalytic Layer is: eelctro-catalyst is dispersed in to ethanol, in ethylene glycol equal solvent, adds appropriate
Figure BDA00002633923000011
as binding agent, fully disperse to form uniform catalyst slurry.This catalyst slurry is by spraying, and the methods such as brushing are prepared in and on diffusion layer, form GDE structure gas-diffusion electrode, or are prepared in the membrane electrode that forms CCM structure in proton exchange membrane.In above-mentioned traditional gas-diffusion electrode or membrane electrode, catalyst granules exists
Figure BDA00002633923000012
under binding agent effect, form loose porous thin layer, the resistance to mass tranfer of reactant in unordered duct is larger, affects battery combination property.
In sum, manufacture the MEA with nano orderedization structured catalysis layer most important for reducing Proton Exchange Membrane Fuel Cells cost and improving proton exchange film fuel battery performance.
Catalytic Layer is prepared in Pt-PDDA self assembly, it is the positive charge group that utilizes PDDA, with the electronegative Pt ion that contains, for example chloroplatinic acid radical ion, by the electrostatic interaction of positive and negative charge, the self assembling process carrying out, then prepares the Pt nano particle of high degree of dispersion by electronation, thereby improves the utilance of Pt to improve decentralization that Pt supports.The method of reporting in document, conventionally adopts and directly carries out self assembly on unordered carbon carrier surface, and stability and the material Transfer performance of Catalytic Layer under high potential is not good.
Summary of the invention
The object of the present invention is 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 adopts following concrete scheme to realize:
A kind of ordering gas-diffusion electrode, comprise gas diffusion layers and the ordering Catalytic Layer based on gas diffusion layers, ordering Catalytic Layer is attached to gas diffusion layers surface, and on microcosmic, has the nanowire array structure perpendicular to the ordered orientation in gas diffusion layers surface direction.
Described ordering Catalytic Layer comprises a kind of conductive polymer nanometer line in the polythiophene of array arrangement on microcosmic or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or polyaniline derivative, and be attached to the PDDA on conductive polymer nanometer line, with the Pt nano particle 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 gcm -2, the loading of Pt nano particle is 0.01-0.5mg cm -2.
Described gas diffusion layers is made up of supporting layer and the microporous layers that is attached to supporting layer one side surface; Described supporting layer is carbon paper or carbon cloth; Described microporous layers be after Vulcan XC-72 carbon dust, acetylene black carbon dust, carbon nano-tube or Graphene mixing PTFE or Nafion by blade coating, brush or be sprayed into support layer surface and make.
The preparation method of described ordering gas-diffusion electrode, comprises following preparation process,
A.PDDA(PDDA) preparation of ordering nanowire array structure of doping
Adopt the method for electro-deposition to have the one in conducting polymer polythiophene or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or the polyaniline derivative of PDDA at the microporous layers surface electrical dopant deposition of gas diffusion layers one side surface or gas diffusion layers, obtain on microcosmic the conductive polymer nanometer linear array structure perpendicular to the PDDA doping of the ordered orientation in diffusion layer surface direction;
B. the self assembly of Catalytic Layer preparation
Be 1-10mg mL by Pt concentration -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps a gained nanowire array structure surface with every square centimeter of 10-100 μ L, under room temperature leave standstill 12-24 hour; 2-10 times of Pt amount of substance Vitamin C aqueous acid or the aqueous solution of sodium borohydride or the aqueous solution of Dimethyl Ammonium borine or hydrazine hydrate are dripped and be applied to above-mentioned conductive polymer nanometer linear array surface, leave standstill 2-10 hour, dry under room temperature after deionized water rinsing, obtain ordering gas-diffusion electrode.
In described step a, electro-deposition method is specially: gas diffusion layers one side be impregnated in and contained in thiophene or pyrroles or aniline or thiophene derivant or azole derivatives or anil solution in electrolyte a kind of, that simultaneously contain supporting electrolyte and PDDA, using gas diffusion layers as work electrode, Pt sheet is as to electrode, saturated calomel electrode, as reference electrode, adopts three-electrode system to carry out electro-deposition.
In step a, in the time that the molecular weight of described PDDA is less than 100,000, the mass concentration of the PDDA aqueous solution is 20-30%; When the molecular weight of described PDDA is less than 200,000 while being more than or equal to 100,000, the concentration of the PDDA aqueous solution is for being greater than 30%, and is less than or equal to 50%;
In step b, the concentration of described chloroplatinic acid aqueous solution is 1-10mgml -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 adding in described electrodeposition process electrolyte solution is one or more in paratoluenesulfonic acid sodium salt, dodecyl sodium sulfate, beta-naphthalenesulfonic-acid, two trimethyl silicon based trifluoroacetamide, 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(vs NHE);
Its electrodeposition time length of described electro-deposition is 0.25-1h.
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 present invention has the following advantages:
1. catalyst stability is high: gas-diffusion electrode of the present invention (comprises the membrane electrode of gas-diffusion electrode and the CCM structure of GDE structure with the membrane electrode that adopts traditional handicraft to prepare, lower same) compare, because Pt catalyst nanoparticles is attached on the conducting polymer that oldered array arranges, have advantages of that catalyst stability is high;
2. catalyst utilization is high: adopt the ordering gas-diffusion electrode prepared of the method for the invention than conventional film electrode, what increased catalyst effectively utilizes area, has improved the unit mass oxygen reducing ability of catalyst;
3. in Catalytic Layer, mass-transfer performance is good: adopt ordering gas-diffusion electrode of the present invention, because its Catalytic Layer is ordering array arrangement, than the unordered Catalytic Layer of arranging of tradition, fuel or the oxidant mass-transfer performance in Catalytic Layer is more excellent;
4. practical: than adopting the substrate grown ordered nano-structures such as other such as silicon, gold, quartz, this method adopts 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 integrality of structure, and conducting polymer is better than material with carbon element in the stability of high potential, the catalyst that can not occur to cause due to carbon corrosion is assembled.
Accompanying drawing explanation
Fig. 1 (a) of the present invention ordering gas-diffusion electrode, (b) traditional gas diffusion electrode structures schematic diagram.As can be seen from the figure,, 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 that is positioned at ordering conducting polymer surface by electrostatic interaction, realize the supporting of polymolecularity of Pt nano particle, improved catalyst loading and be exposed to the catalyst ratio that surface can effectively utilize; 3. the array arrangement forming in ordering gas-diffusion electrode (a) is conducive to reactant and product at the mass transfer of Catalytic Layer, is conducive to improve the utilance of reactant, thereby improves battery performance.
A kind of electromicroscopic photograph (embodiment 1) of the method for the invention after diffusion layer surface electrical depositing electrically conductive polymer P Py that adopt of Fig. 2; Can find out that PPy nano wire presents perpendicular to surperficial oldered array structure on the microporous layers surface of gas diffusion layers, improve Pt particle and effectively supported area, and the passage that carries out active principle transmission is provided.
Fig. 3 is a kind of adopts the electromicroscopic photograph (embodiment 1) of the ordering gas-diffusion electrode after catalyst-loaded that the method for the invention makes; Can find out, Pt nano particle distributes at PPy surface uniform, presents the Particle Cluster of reunion in the site that has PDDA, makes Pt particle effectively be exposed to three-phase reaction interface, has improved the utilance of Pt particle.
Fig. 4 is the cyclic voltammetry curve of the commodity E-Tek catalyst (b) in ordering membrane electrode catalyst (a) and comparative example 1 in embodiment 1, and electrolyte solution is N 2saturated 0.5M sulfuric acid solution, sweeping the rate of hastening is 50mVs -1.Can find out from the result of calculation of this figure, in embodiment 1, the electro-chemical activity surface area of ordering membrane electrode catalytic layer can reach 55.4 square metres of every gram of platinum, 39.6 square metres of every gram of platinum of electro-chemical activity surface area compared to commercial catalyst in comparative example 1 have improved 40%, and catalyst utilization significantly improves.
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 the Catalytic Layer of burn-in test front and back; Wherein electrolyte solution is the 0.5M sulfuric acid solution that N2 is saturated, and sweep limits is 0.85-1.2V vs.NHE, and sweep speed is 200mVs -1, the scanning number of turns is 1000 circles.As can be seen from the figure, through the scanning of 1000 circles, in ordering gas-diffusion electrode Catalytic Layer the electro-chemical activity surface area of catalyst can remain on before burn-in test more than 60%, and the electro-chemical activity surface area of E-Tek catalyst is down to 40% left and right before burn-in test in traditional gas-diffusion electrode Catalytic Layer, this is mainly because the catalyst carrier in ordering gas-diffusion electrode is conducting polymer, and conducting polymer is not perishable under high potential, therefore, its stability is than the good stability of carbon supported catalyst in traditional gas-diffusion electrode, illustrate that this ordering gas diffusion electrode structures has played important function for the stability that keeps catalyst.
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 O 2saturated 0.5M sulfuric acid solution, sweep speed is 20mVs -1.As can be seen from the figure, through the scanning of 1000 circles, catalyst hydrogen reduction half wave potential decline 8mV left and right in ordering gas-diffusion electrode Catalytic Layer, and in traditional gas-diffusion electrode Catalytic Layer more than the hydrogen reduction half wave potential decline 20mV of E-Tek catalyst, this is mainly because the catalyst carrier in ordering gas-diffusion electrode is conducting polymer, and conducting polymer is not perishable under high potential, therefore its stability is than the good stability of carbon supported catalyst in traditional gas-diffusion electrode, illustrate that in this ordering gas-diffusion electrode, structure has played important function for the catalytic oxidation-reduction stability that keeps catalyst.
Embodiment
Below by example, the present invention is described in detail, but the present invention is not limited only to following examples.
Embodiment 1:
1) preparation of gas diffusion layers:
Toray carbon paper is soaked in the PTFE aqueous solution of mass concentration 20%, fully infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
2) preparation of ordering gas-diffusion electrode:
A. the preparation of the ordering nanowire array structure of finishing
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and in plastic clamp, insert a conduction platinized platinum, guarantee that conduction platinized platinum contacts well with gas diffusion layers simultaneously.Said apparatus is placed in to three electrode electro-deposition systems, contacting good conduction platinized platinum with gas diffusion layers is work electrode, saturated calomel electrode is to electrode and reference electrode, electrolyte is for containing 0.1M pyrroles, 0.1M paratoluenesulfonic acid sodium salt, mass concentration is 1% Ultra-low molecular weight (MW<100, 000) the 0.2M phosphate buffer of PDDA, on conduction platinized platinum, apply operating voltage 0.65V(vs SCE), duration 30min, form the polypyrrole (PPy) of the doping PDDA of one deck ordering array arrangement in gas diffusion layers surface electrical deposition, be labeled as PDDAPPy-GDL sample.
B. the self assembly of Catalytic Layer preparation
To be 7.4mg mL containing Pt amount -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps 2 by every square centimeter of 20 μ L) the conducting polymer surface of a gained PDDAPPy-GDL sample, leave standstill 24 hours.Be 37mg mL by concentration -1aqueous ascorbic acid drip and be applied to above-mentioned conducting polymer surface that has been coated with the PDDAPPy-GDL sample of chloroplatinic acid according to every square centimeter of 20 μ L equally, leave standstill 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the conducting polymer surface of the PDDAPPy-GDL sample that has supported catalyst with deionized water, after air-dry 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 infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
The rare powder ultrasonic of graphite prepared by dilatometry is scattered in ethanolic solution, slurries is supported in above-mentioned gas diffusion layer microporous layers surface with knife coating, weighs, until carrying capacity is 0.2mg cm -2.Obtain the gas diffusion layers of the rare modification of graphite.
2) preparation of ordering gas-diffusion electrode:
A. the preparation of the ordering nanowire array structure of finishing
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and in plastic clamp, insert a conduction platinized platinum, guarantee conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in to three electrode electro-deposition systems, electrolyte is to contain 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, on conduction platinized platinum, apply operating voltage 0.65V(vs SCE), duration 30min, the polypyrrole (PPy) that forms the doping PDDA of one deck ordering array arrangement in gas diffusion layers surface electrical deposition, is labeled as PDDAPPy-GDL sample.
B. the self assembly of Catalytic Layer preparation
To be 7.4mg mL containing Pt amount -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps 2 by every square centimeter of 20 μ L) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, leaves standstill 24 hours.Be 37mg mL by concentration -1aqueous ascorbic acid drip and be applied to above-mentioned electrode surface that is coated with chloroplatinic acid according to every square centimeter of 20 μ L equally, leave standstill 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface that has supported catalyst with deionized water, after air-dry 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 infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
Multi-walled carbon nano-tubes powder ultrasonic standby chemical meteorology deposition legal system is scattered in ethanolic solution, slurries is supported in above-mentioned gas diffusion layer microporous layers surface with knife coating, weigh, until carrying capacity is 0.2mg cm -2.Obtain carbon nano tube modified gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure of finishing
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and in plastic clamp, insert a conduction platinized platinum, guarantee conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in to three electrode electro-deposition systems, electrolyte is to contain 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, on conduction platinized platinum, apply operating voltage 0.65V(vs SCE), duration 30min, the polypyrrole (PPy) that forms the doping PDDA of one deck ordering array arrangement in gas diffusion layers surface electrical deposition, is labeled as PDDAPPy-GDL sample.
B. the self assembly of Catalytic Layer preparation
To be 7.4mg mL containing Pt amount -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps 2 by every square centimeter of 20 μ L) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, leaves standstill 24 hours.Be 37mg mL by concentration -1aqueous ascorbic acid drip and be applied to above-mentioned electrode surface that is coated with chloroplatinic acid according to every square centimeter of 20 μ L equally, leave standstill 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface that has supported catalyst with deionized water, after air-dry 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 infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure of finishing
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and in plastic clamp, insert a conduction platinized platinum, guarantee conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in to three electrode electro-deposition systems, electrolyte is to contain 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, on conduction platinized platinum, apply operating voltage 0.75V(vs SCE), duration 60min, the polypyrrole (PPy) that forms the doping PDDA of one deck ordering array arrangement in gas diffusion layers surface electrical deposition, is labeled as PDDAPPy-GDL sample.
B. the self assembly of Catalytic Layer preparation
To be 7.4mg mL containing Pt amount -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps 2 by every square centimeter of 40 μ L) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, leaves standstill 24 hours.Be 37mg mL by concentration -1aqueous ascorbic acid drip and be applied to above-mentioned electrode surface that is coated with chloroplatinic acid according to every square centimeter of 40 μ L equally, leave standstill 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface that has supported catalyst with deionized water, after air-dry 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 infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure of finishing
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and in plastic clamp, insert a conduction platinized platinum, guarantee conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in to three electrode electro-deposition systems, electrolyte is to contain 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, on conduction platinized platinum, apply operating voltage 0.6V(vs SCE), duration 20min, the polypyrrole (PPy) that forms the doping PDDA of one deck ordering array arrangement in gas diffusion layers surface electrical deposition, is labeled as PDDAPPy-GDL sample.
B. the self assembly of Catalytic Layer preparation
To be 7.4mg mL containing Pt amount -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps 2 by every square centimeter of 10 μ L) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, leaves standstill 24 hours.Be 37mg mL by concentration -1aqueous ascorbic acid drip and be applied to above-mentioned electrode surface that is coated with chloroplatinic acid according to every square centimeter of 10 μ L equally, leave standstill 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface that has supported catalyst with deionized water, after air-dry 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 infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
2) preparation of ordering membrane electrode:
A. the preparation of the ordering nanowire array structure of finishing
By above-mentioned steps 1) gained gas diffusion layers is placed in plastic clamp, and in plastic clamp, insert a conduction platinized platinum, guarantee conduction platinized platinum and gas diffusion layers good contact simultaneously.Said apparatus is placed in to three electrode electro-deposition systems, electrolyte is to contain 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, on conduction platinized platinum, apply operating voltage 0.65V(vs SCE), duration 30min, the polypyrrole (PPy) that forms the doping PDDA of one deck ordering array arrangement in gas diffusion layers surface electrical deposition, is labeled as PDDAPPy-GDL sample.
B. the self assembly of Catalytic Layer preparation
To be 7.4mg mL containing Pt amount -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps 2 by every square centimeter of 20 μ L) a gained grown on the gas diffusion layers of orderly conductive polymer nanometer structure, leaves standstill 24 hours.Be 37mg mL by concentration -1aqueous ascorbic acid drip and be applied to above-mentioned electrode surface that is coated with chloroplatinic acid according to every square centimeter of 20 μ L equally, leave standstill 4 hours.Until surface liquid color is become colorless after clear solution by glassy yellow, repeatedly rinse the Ordered Film electrode surface that has supported catalyst with deionized water, after air-dry 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 infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
2) preparation of catalyst slurry:
3mg commodity platinum C catalyst (E-Tek) is placed in to beaker, adds 50mg deionized water, ultrasonic dispersion 5 minutes.Add again the Nafion solution (DuPont) of 7mg5%, ultrasonic dispersion 5 minutes.Add 50mg absolute ethyl alcohol, ultrasonic dispersion 30 minutes, obtains catalyst slurry.
3) preparation of Catalytic Layer:
By above-mentioned steps 1) gained sample is fixed on Vacuum Heat platform, is heated to 60 ℃, after 30 minutes, takes off and weighs, retighten on hot platform; Get above-mentioned by step 2) gained catalyst slurry is evenly sprayed at step 1 with nitrogen airbrush) gained sample surfaces, after spraying finishes, at 60 ℃, keep 30 minutes, take off and weigh, catalyst loading is about 0.5mgcm -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 infiltrates rear taking-up air-dry, weigh.Repeatedly carry out above-mentioned steps, process rear carbon paper quality until PTFE carrying capacity is 15%(hydrophobization) left and right.By Vulcan XC-72 carbon dust with respect to carbon dust and PTFE quality and 10% mass concentration 20%PTFE aqueous solution even, after diluting with the ethanol of 20 times of carbon dust quality, under ultrasound condition, disperse 20 minutes, stir.The carbon paper of above-mentioned hydrophobization processing is placed on glass plate and is fixed, above-mentioned slurries blade coating, in carbon paper surface, is weighed, until carbon dust carrying capacity is 1mg cm -2, obtain gas diffusion layers.
2) preparation of catalyst slurry:
3mg commodity platinum black catalyst (JM) is placed in to beaker, adds 50mg deionized water, ultrasonic dispersion 5 minutes.Add again the Nafion solution (DuPont) of 7mg5%, ultrasonic dispersion 5 minutes.Add 50mg absolute ethyl alcohol, ultrasonic dispersion 30 minutes, obtains catalyst slurry.
3) preparation of Catalytic Layer:
By above-mentioned steps 1) gained sample is fixed on Vacuum Heat platform, is heated to 60 ℃, after 30 minutes, takes off and weighs, retighten on hot platform; Get above-mentioned by step 2) gained catalyst slurry is evenly sprayed at step 1 with nitrogen airbrush) gained sample surfaces, after spraying finishes, at 60 ℃, keep 30 minutes, take off and weigh, catalyst loading is about 0.5mgcm -2.Obtain traditional structure membrane electrode.

Claims (9)

1. an ordering gas-diffusion electrode, is characterized in that:
Comprise gas diffusion layers and the ordering Catalytic Layer based on gas diffusion layers, ordering Catalytic Layer is attached to gas diffusion layers surface, and on microcosmic, has the nanowire array structure perpendicular to the ordered orientation in gas diffusion layers surface direction.
2. ordering gas-diffusion electrode as claimed in claim 1, is characterized in that:
Described ordering Catalytic Layer comprises a kind of conductive polymer nanometer line in the polythiophene of array arrangement on microcosmic or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or polyaniline derivative, and be attached to the PDDA on conductive polymer nanometer line, with the Pt nano particle 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 nano particle is 0.01-0.5mg cm -2.
3. ordering gas-diffusion electrode as claimed in claim 1, is characterized in that:
Described gas diffusion layers is made up of supporting layer and the microporous layers that is attached to supporting layer one side surface;
Described supporting layer is carbon paper or carbon cloth; Described microporous layers be after Vulcan XC-72 carbon dust, acetylene black carbon dust, carbon nano-tube or Graphene mixing PTFE or Nafion by blade coating, brush or be sprayed into support layer surface and make.
4. a preparation method for the arbitrary described ordering gas-diffusion electrode of claim 1-2, is characterized in that: comprise following preparation process,
A.PDDA(PDDA) preparation of ordering nanowire array structure of doping
Adopt the method for electro-deposition to have the one in conducting polymer polythiophene or polythiofuran derivative or polypyrrole or Polypyrrole derivatives or polyaniline or the polyaniline derivative of PDDA at the microporous layers surface electrical dopant deposition of gas diffusion layers one side surface or gas diffusion layers, obtain on microcosmic the conductive polymer nanometer linear array structure perpendicular to the PDDA doping of the ordered orientation in diffusion layer surface direction;
B. the self assembly of Catalytic Layer preparation
Be 1-10mg mL by Pt concentration -1chloroplatinic acid aqueous solution drip and be applied to above-mentioned steps a gained nanowire array structure surface with every square centimeter of 10-100 μ L, under room temperature leave standstill 12-24 hour; 2-10 times of Pt amount of substance Vitamin C aqueous acid or the aqueous solution of sodium borohydride or the aqueous solution of Dimethyl Ammonium borine or hydrazine hydrate are dripped and be applied to above-mentioned conductive polymer nanometer linear array surface, leave standstill 2-10 hour, dry under room temperature after deionized water rinsing, obtain ordering gas-diffusion electrode.
5. the preparation method of ordering gas-diffusion electrode as claimed in claim 4, is characterized in that:
In described step a, electro-deposition method is specially: gas diffusion layers one side be impregnated in and contained in thiophene or pyrroles or aniline or thiophene derivant or azole derivatives or anil solution in electrolyte a kind of, that simultaneously contain supporting electrolyte and PDDA, using gas diffusion layers as work electrode, Pt sheet is as to electrode, saturated calomel electrode, as reference electrode, adopts three-electrode system to carry out electro-deposition.
6. the preparation method of ordering membrane electrode as claimed in claim 4, is characterized in that:
In step a, in the time that the molecular weight of described PDDA is less than 100,000, the mass concentration of the PDDA aqueous solution is 20-30%; When the molecular weight of described PDDA is less than 200,000 while being more than or equal to 100,000, the concentration of the PDDA aqueous solution is for being greater than 30%, and is less than or equal to 50%;
In step b, the concentration of described chloroplatinic acid aqueous solution is 1-10mgml -1.
7. the preparation method of ordering gas-diffusion electrode as described in claim 4 or 5, is characterized 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 adding in described electrodeposition process electrolyte solution is one or more in paratoluenesulfonic acid sodium salt, dodecyl sodium sulfate, beta-naphthalenesulfonic-acid, two trimethyl silicon based trifluoroacetamide, 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(vs NHE);
Its electrodeposition time length of described electro-deposition is 0.25-1h.
8. the preparation method of ordering gas-diffusion electrode as described in claim 4 or 5, is characterized in that:
In described electrolyte, the mass concentration of PDDA is 0.05-5%.
9. an application for ordering gas-diffusion electrode described in claim 1, is characterized in that:
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.
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