CN1954392A - Low platinum fuel cells, catalysts, and method for preparing the same - Google Patents

Low platinum fuel cells, catalysts, and method for preparing the same Download PDF

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CN1954392A
CN1954392A CNA2005800111291A CN200580011129A CN1954392A CN 1954392 A CN1954392 A CN 1954392A CN A2005800111291 A CNA2005800111291 A CN A2005800111291A CN 200580011129 A CN200580011129 A CN 200580011129A CN 1954392 A CN1954392 A CN 1954392A
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catalyst
fuel
nano particle
film
alloy
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王宁
董翊
李依群
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Intematix Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

This invention provides novel fuel cell catalysts comprising new series of catalytically active thin-film metal alloys with low platinum concentration supported on nanostructured materials (nanoparticles). In certain embodiments, an integrated gas-diffusion/electrode/catalyst layer can be prepared by processing catalyst thin films and nanoparticles into gas-diffusion media such as Toray or SGL carbon fiber papers. The catalysts can be placed in contact with an electrolyte membrane for PEM fuel cell applications.

Description

Low platinum fuel cells, Catalysts and its preparation method
The cross reference of related application
The application is in the further part of the USSN 10/898669 of submission on July 23rd, 2004, USSN10/898669 is in the further part of the USSN 10/823088 of submission on April 12nd, 2004, USSN 10/823088 requires in priority and the rights and interests of the USSN 60/549712 of submission on March 2nd, 2004, and the full content of above-mentioned all applications is in order all to be incorporated into this by reference.
Relate to the statement of the right of the present invention of under the research and development of federal funding, carrying out
[nothing]
Invention field
The field is for being used for the electrochemical catalyst field of fuel cell (for example, polymer dielectric film (PEM) fuel cell) under the present invention.The present invention relates to reduce platinum content, the raising catalytic efficiency by nanostructure of the carbon monoxide-olefin polymeric of innovating and the electrode that constitutes fuel cell and interface between the polymer dielectric (PEM) or gas differential diffusing (little diffusion) layer inside.
Background of invention
Fuel cell makes the combination under the situation of not burning of hydrogen and oxygen form water, produces direct current.This process can be described as the inverse process of electrolysis.Fuel cell has and is used for fixing or the prospect of compact power articles for use; But the commercial viability that fuel cell is used to generate electricity in fixing and portable articles for use depends on the solution of a plurality of problems such as manufacturing, cost and durability.
Electrochemical fuel cell is converted into electric power and product with fuel and oxidant.Typical fuel cell is made up of a barrier film and two electrodes that are called negative electrode and anode.Barrier film as sandwich structure between negative electrode and anode.Anode provides the fuel of hydrogen form, reacts below the catalyst of anode place platinum and alloy thereof and so on: 2H2 → 4H ++ 4e -
At the anode place, hydrogen is decomposed into hydrogen ion (proton) and electronics.Proton is moved to negative electrode from anode by barrier film.Electronics moves out from anode with the form of electric current by external circuit.Providing form to negative electrode is oxygen or the oxidant that contains the oxygen air, and at the negative electrode place, this oxidant by the hydrogen ion of barrier film and the electron reaction of coming from the external circuit migration, forms the liquid water of product with.Reaction is by platinum group metal catalyzed.The reaction that the negative electrode place takes place is as follows: O 2+ 4H ++ 4e -→ 2H 2O.
People have proved first that chemical energy can successfully be converted into electric energy in the original fuel battery before 160 years.But although fuel cell technology has attracting system effectiveness and environmental advantages, the verified industrial products that early stage scientific experiment result is developed as viable commercial are difficult.The problem that is usually directed to is to lack suitable material, the power technology competition that can make the cost of generating and efficient and exist.
In the past few years, polymer electrolyte fuel cells is being obtained significant improvement aspect efficient and the utility fuel battery design.More verified be used for the prototype of the fuel cell substitute of portable battery pack and automobile batteries group.But the problem relevant with the stability of cost, activity and eelctro-catalyst becomes the subject matter of polymer electrolyte fuel cells development.For example, platinum (Pt) is catalyst based is the most successful catalyst that is used for fuel cell and other catalysis articles for use.But, platinum expensive and rarely limited the use of this material in large-scale application unfortunately.
In addition, anode is owing to anthracemia, and also oneself becomes a problem in the platinum use.In negative electrode one side, usually need higher catalytic amount, because the fuel that contains methyl alcohol and other carbon compound reacts on negative electrode with oxygen under the catalytic action of platinum by barrier film, thereby reduced the efficient of fuel cell.
In order to improve catalytic efficiency and to reduce cost, use other noble metal and base metal to form platinum alloy as catalyst.Studied the noble metal that comprises Pd, Rh, Ir, Ru, Os, Au etc.Also attempted comprising the base metal of (United States Patent (USP)s 6562499) such as Sn, W, Cr, Mn, Fe, Co, Ni, Cu.Disclosed the act as a fuel catalyst of battery applications of different platinum alloy.Bianry alloy as catalyst comprises Pt-Cr (United States Patent (USP) 4316944), Pt-V (United States Patent (USP) 4202934), Pt-Ta (United States Patent (USP) 5183713), Pt-Cu (United States Patent (USP) 4716087), Pt-Ru (United States Patent (USP) 6007934), Pt-Y (United States Patent (USP) 4031291) etc.Ternary alloy three-partalloy as catalyst comprises Pt-Ru-Os (United States Patent (USP) 5856036), Pt-Ni-Co, Pt-Cr-C, Pt-Cr-Ce (United States Patent (USP) 5079107), Pt-Co-Cr (United States Patent (USP) 4711829), Pt-Fe-Co (United States Patent (USP) 4794054), Pt-Ru-Ni (United States Patent (USP) 6517965), Pt-Ga-Cr, Co, Ni (United States Patent (USP) 4880711), Pt-Co-Cr (United States Patent (USP) 4447506) etc.Quaternary alloy as catalyst comprises Pt-Ni-Co-Mn (United States Patent (USP) 5225391), Pt-Fe-Co-Cu (United States Patent (USP) 5024905) etc.In anode one side, the malicious on the decrease problem of Ru aspect plays important effect (Journal of The Electrochemical Society, (149 (7) A862-A867,2002) (United States Patent (USP) 6339038).Ru has the ability that forms OHads from water.This makes CO be transformed into CO by the catalysis desorption 2In negative electrode one side, used the base metal complex compound catalyst, such as Fe, Co, Ni porphyrin (Solid State Ionics 148 (2002) 591-599).
In the electrode design field,, need the three phase boundary of reacting gas (H2 and O2), catalyst and conductor (for proton and electronics) usually for electrochemical reaction.The manufacture method of widely used fuel cell is so-called " printing ink " coating.In the method, catalyst granules (for example, the 2-4 nanometer) loads on the carbon granule (15 nanometers, Vulcan XC72).These particles mix as printing ink with the solution of polyeletrolyte, this printing ink are spread upon on the surface of conductor such as carbon paper, form the three-phase coating.In the method, dielectric film has covered the hybrid particles of catalyst and carbon.Therefore, in this structure, there is not direct three phase boundary to exist.Reacting gas H 2And O 2Not direct contact catalyst, but must diffuse through dielectric substrate, arrive catalyst surface.In negative electrode one side, proton must diffuse through dielectric substrate, to touch O 2-Ion.Therefore, have two kinds of opposite requirements: proton needs thick dielectric substrate keeping good conductivity, and on the other hand, thick dielectric substrate can form O 2Diffusion hinder.In order to solve this difficulty, existing suggestion is done some improvement to the design of " printing ink " coating.The pure electrolyte bundle that is inserted in " printing ink " coating is used in Toyata company (at United States Patent (USP) 6,015,635 in) suggestion, improves proton conductivity.In United States Patent (USP) 6309772, suggestion will mix with the carbon-catalyst granules that is not coated with through electrolyte through the carbon-catalyst granules of electrolyte coating, forms " printing ink " layer, improves gaseous diffusion.In these " printing ink " coating structures, the efficient of catalyst still is subjected to the restriction of gas and diffusion of protons.
Recently, some new catalyst structures are used to improve catalytic efficiency.For example, 3M company (United States Patent (USP) 5,879,827 and 6,040,077) uses the electrode of nanostructure.In this structure, the catalysed particulate of the acicular nanometer level of deposition in the brilliant load of the nanometer polymer of needle-like palpus.At first, depositing organic material on base material.Then this sedimentary deposit is annealed in a vacuum, form the closely spaced array of acicular nanometer polymer whisker.Preferably must brilliant length be equal to or less than 1 micron.Deposited catalyst film on load must crystalline substance then.The diameter of catalyst granules is less than 10 nanometers, and length is less than 50 nanometers.In the Pt and Ru loading range of 0.09-0.425 milligram/square centimeter, fuel cell obtains satisfied catalytic efficiency.But, owing to need nonconducting nanometer polymer palpus brilliant, and the polymer whisker layer that has been coated with catalyst need be transferred on the carbon electrode, so this method is complicated.In this design, below the palpus crystal layer, still use the carbon printing ink that is mixed with Pt.
Gore Enterprise Holdings (United States Patent (USP) 6,287,717 and 6,300,000) uses at carbon electrode or is mixed with direct catalyst film coating on the carbon printing ink layer of Pt.This catalyst film plays an important role as boundary layer, and this boundary layer has the platinum concentration different with all the other catalyst layers.This structure has reduced the platinum content of used catalyst in the fuel cell effectively.The load of declaring catalyst is less than 0.1 milligram/square centimeter.
Summary of the invention
The invention provides novel fuel-cell catalyst, this catalyst comprises the new range film metal alloy catalyst of the low platinum concentration that loads on the nano structural material (nano particle).In some embodiments, by catalyst film and nano particle being handled the gaseous diffusion/electrode/catalyst layer for preparing integration in the gas diffusion medias such as Toray or SGL carbon fiber paper, carbon cloth, porous electrode.Catalyst can be placed into and the dielectric film position contacting that is used for PEM fuel cell articles for use.
Like this, in one embodiment, the invention provides a kind of composition, it comprises a plurality of loads has nano particle (for example, nanotube, nanofiber, nanometer prominent (nanohorns), nano powder, nanosphere, quantum dot etc.) conductive fiber (for example, carbon fiber, metallic fiber, porous electrode etc.).In some embodiments, conductive fiber itself is not nano particle or nanofiber.A plurality of fibers comprise porous electrode and/or carbon paper, carbon cloth, carbon impregnated polymer, porous conductive polymer, porous metals conductor etc.In some embodiments, nano particle comprises carbon nano-tube, and this nanotube is selected from following nanotube growth catalyst with one or more and forms crystal seed (seeded): Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.Some preferred nanotube growth catalyst comprises, but is not limited to Co 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2In different execution modes, nano particle is a length less than 50 microns and/or width/diameter less than about 100 nanometers or less than the nanotube of about 50 nanometers.Usually be coated with basic continuous films on the nano particle, preferably the catalytic activity film for example, comprises the film of platinum or platinum alloy.This film can partly or cover nano particle continuously, and in some embodiments, thickness range is about 1 to 1000 dust, more generally is about 5 to 100 or 500 dusts.
In some embodiments, film comprises a kind of alloy, and this alloy comprises that platinum (Pt), vanadium (V) and one or more are selected from Co, Ni, Mo, Ta, W and Zr, more generally are selected from the metal of Co and Ni.In some embodiments, platinum accounts for 12%, 25% or 50% (mol ratio or atomic percent) at most in alloy.In some embodiments, alloy contains platinum, vanadium, nickel and copper.In some embodiments, to comprise a kind of general formula be Pt to film xV yCo zNi wAlloy, wherein x is greater than 0.06 and less than 1; Y, z and w are respectively greater than 0 and less than 1; And x+y+z+w=1.In some embodiments, x is 0.12.In some embodiments, x is 0.12, and y is 0.07, and z is 0.56, and w is 0.25.
The present invention also provides a kind of fuel-cell catalyst that comprises a plurality of nano particles, is being coated with continuous substantially catalytic activity film on this nano particle, for example comprises the film of platinum or platinum alloy.In some embodiments, nano particle is a nanotube.This nanotube is selected from following nanotube growth catalyst with one or more and forms crystal seed: Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.Particularly preferred nanotube growth catalyst comprises, but is not limited to Co 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2In different execution modes, the length of nanotube less than 50 microns and/or width/diameter less than about 100 nanometers or less than about 50 nanometers.Film can partly or cover nano particle continuously, and in some embodiments, thickness range is about 1 to 1000 dust, more generally is about 5 to 100 or 500 dusts.
In some embodiments, film comprises a kind of alloy, and this alloy comprises that platinum (Pt), vanadium (V) and one or more are selected from Co, Ni, Mo, Ta, W and Zr, more generally are selected from the metal of Co and Ni.In some embodiments, platinum accounts for 12%, 25% or 50% (mol ratio or atomic percent) at most in alloy.In some embodiments, alloy contains platinum, vanadium, nickel and copper.In some embodiments, to comprise a kind of general formula be Pt to film xV yCo zNi wAlloy, wherein x is greater than 0.06 and less than 1; Y, z and w are respectively greater than 0 and less than 1; And x+y+z+w=1.In some embodiments, x is 0.12.In some embodiments, x is 0.12, and y is 0.07, and z is 0.56, and w is 0.25.In some embodiments, nano particle is attached to or is attached in the base material (for example, porous carbon base material, polymeric substrate, carbon paper etc.).Nano particle can be electrically connected on the electrode.In some embodiments, nano particle be selected from that nanotube, nanofiber, nanometer are prominent, nano powder, nanosphere and quantum dot.In some embodiments, nano particle is to be selected from the carbon nano-tube that following catalyst forms crystal seed: Fe with one or more xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.In some embodiments, nano particle is to be selected from the carbon nano-tube that following catalyst forms crystal seed: Co with one or more 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2In some embodiments, nano particle is a length less than about 200 microns, the width nanotube less than about 100 nanometers.In some embodiments, nano particle is the nanotube that diameter is about 10 nanometer to 100 nanometers.
In another embodiment, the invention provides a kind of electrode-barrier film combination, it comprises: at least one comprises first conductive electrode of first fuel-cell catalyst; At least one comprises second conductive electrode of second fuel-cell catalyst; The proton exchange membrane that first conductive electrode and second conductive electrode are separated; Described first fuel-cell catalyst and second fuel-cell catalyst (for example are independently selected from the catalyst described in the literary composition, a plurality of nano particles, wherein said nano particle is being coated with continuous substantially catalytic activity film, for example, comprises the film of platinum or platinum alloy).Described first fuel-cell catalyst and second fuel-cell catalyst can comprise identical or different nano particle and/or identical or different catalytic activity film.In some embodiments, the thickness of proton exchange membrane is about 2 microns to 100 microns.Suitable proton exchange membrane includes, but not limited to (PPO), SiO 2-polymer compound of Nafion, silicon dioxide Nafion compound, poly phosphazene, sulfonation etc.In some embodiments, first conductive electrode and first fuel-cell catalyst form separator.In some embodiments, first conductive layer and first fuel-cell catalyst also comprise the little diffusion layer between electrode and catalyst.In some embodiments, the simple layer of first conductive electrode and first fuel-cell catalyst formation integration (for example, IGEC).Therefore, in some embodiments, first fuel-cell catalyst also can be used as little diffusion layer.In some embodiments, second conductive layer and second fuel-cell catalyst also comprise the little diffusion layer between electrode and catalyst.In some embodiments, the simple layer of second conductive electrode and second fuel-cell catalyst formation integration (for example, IGEC).Therefore, in some embodiments, second fuel-cell catalyst also can be used as little diffusion layer.
The present invention also provides a kind of fuel cell pack, and it comprises the electrode diaphragm combination (membrane electrode assembly (MEA)) of the electrical connection described in a plurality of literary compositions.The present invention also provides the electric device that comprises one or more this fuel cell packs.In addition, the invention provides a kind of battery pack substitute, described battery pack substitute comprises the shell that holds fuel cell pack described in the literary composition, and shell is provided for the positive terminal and the negative pole end of the device of contact need electric power.In some embodiments, the battery pack substitute can be given house, mobile phone, illuminator, computer and/or utensil power supply.
In some embodiments, the invention provides the method for making fuel catalyst.This method generally includes following steps: a plurality of nano particles are provided; On nano particle, deposit continuous substantially catalytic activity film, for example comprise the film of platinum or platinum alloy.This electroless copper deposition operation can be any suitable method, includes but not limited to sputtering sedimentation, chemical vapor deposition (CVD), molecular beam epitaxy (MBE), the auxiliary vapour deposition of plasma and electron-beam evaporation.Film can partly or entirely cover nano particle.In some embodiments, nano particle is the nanotube that comprises the catalyst of nanotube growth described in the literary composition.Film generally includes any metal or metal alloy described in the literary composition, in the described in the text usually scope of thickness.Nano particle can be attached on the base material (for example, one or more carbon fibers, porous carbon base material, porous electrode etc.).Suitable nano particle includes, but not limited to that nanotube, nanofiber, nanometer are prominent, nano powder, nanosphere and quantum dot.Some preferred embodiment in, nano particle is the carbon nano-tube described in the literary composition.
The present invention also provides the method for preparing fuel cell component.This method generally includes following steps: a plurality of fibers and/or porous electrode material are provided; Deposit nanometric particles catalyst on a plurality of fibers and/or porous electrode material; Use nanoparticle catalyst on a plurality of fibers and/or porous electrode material, to form nano particle; Formation comprises the catalytic active layer of basic continuous films on nano particle, thereby forms a kind of fuel cell component, and this element contains the fiber that the nano particle that partly or entirely is coated with the catalytic activity film in a plurality of loads.In some embodiments, described a plurality of fiber comprises a plurality of carbon fibers (for example, carbon fiber paper or other porous carbon electrodes).In some embodiments, nanoparticle catalyst is a carbon nano-tube catalyst, for example described in the literary composition, and/or nano particle is carbon nano-tube, for example described in the literary composition, and/or basic continuous films is the catalytic activity film, for example described in the literary composition.In some embodiments, form nano particle by chemical vapor deposition (CVD).In some embodiments, the deposit nanometric particles catalyst comprises catalyst is deposited on the fiber by the chemical vapor deposition (CVD) method.Some preferred embodiment in, the nanotube growth catalyst is to be selected from following catalyst: Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.Some appropriate catalyst includes, but not limited to Co 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2In some embodiments, provide a plurality of fibers and/or porous electrode material to comprise carbon fiber paper is provided; The deposit nanometric particles catalyst comprises by chemical vapour deposition technique and deposits described catalyst; Form nano particle and comprise the formation carbon nano-tube; Form catalytic active layer and comprise that deposition contains the basic continuous films of platinum or platinum alloy.
The present invention also provides a kind of method of making fuel cell with carbon nano-tube.This method generally includes following steps: the nanotube growth catalyst is provided, and it is selected from: Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein; On described catalyst, form carbon nano-tube (for example, passing through CVD).In some embodiments, catalyst is to be selected from following catalyst: Co 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
The present invention also provides a kind of carbon nano-tube, and it comprises and is selected from following nanotube growth catalyst: Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.In some embodiments, catalyst is to be selected from following catalyst: Co 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
The present invention also provides appropriate carbon nanotube growth catalysts (for example, being used for the fuel cell carbon nano tube growth).Preferred catalyst comprises and is selected from following catalyst: Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.In some embodiments, catalyst is to be selected from following catalyst: Co 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
Definition
In the literary composition used term " nano particle " refer to size be equal to or less than at least about 500 nanometers, preferably be equal to or less than about 100 nanometers, more preferably be equal to or less than about 50 or 20 nanometers, perhaps crystal size is equal to or less than the particle of about 10 nanometers, and above-mentioned numerical value is recorded by the diffraction half-peak breadth of electron micrograph image and/or the scanning of standard 2-θ X-ray diffraction.
Term " membrane electrode assembly (MEA) " and " membrane electrode assemblies " replaceable use are often referred at least two electrodes that separated by PEM.
Term " electrical connection " refers to a kind of like this connection when relating to nano particle (for example nanoparticle catalyst) with electrode, promptly electronics or proton can be delivered to electrode or from the electrodes transfer to the nano particle from nano particle by this connection.Being electrically connected not necessarily needs between nano particle and electrode actual physical taking place and contacts.Therefore be electrically connected and include, but not limited to direct conductivity, electron tunneling effect, inductance coupling high etc.
Term " continuous substantially " forms the film of coating quite uniformly when referring on being present in nano particle when being used for describing " being coated with the nano particle of basic continuous films ".This with look block or spherical film different.This coating can not seem that class refutes or rugged.In some embodiments, film cover substantially continuously nano particle the surface at least 20%, preferably at least 30% or 40%, more preferably at least 50% or 60%, most preferably at least 70% or 80%.
Term " load " refers to when being used to mention " carbon fiber that nano particle in a plurality of loads " that nano particle is attracted on the fiber and/or by chemical bond (for example, ionic, hydrophobic type or covalent type) and/or be inserted in the fiber or in the space between the fiber.
Term " gaseous diffusion/electrode of integration/catalyst (IGEC) " refers to porous (gas-diffusion electrode), and it contains the nano particle that the continuous substantially catalytic activity film of all or part of quilt (for example, platinum or platinum alloy film) covers.In some embodiments, IGEC is also as little diffusion device of integrating.
Term " fuel cell component " refers to comprise the integrated element of the structure that can be used for making up fuel cell.In some embodiments, " fuel cell component " is IGEC.
Term " fuel-cell catalyst " refers to be used for the catalytically-active materials (for example, platinum or platinum alloy) of fuel cell or is coated with the nano particle of catalytically-active materials film.Therefore, for example, in some embodiments, fuel-cell catalyst comprises a plurality of nano particles, and described nano particle is coated with the basic continuous films that comprises platinum or platinum alloy.From literary composition, can be well understood to its concrete application.
Term " nanoparticle catalyst " refers to the material as " crystal seed " of catalyst and/or nucleating point and/or beginning and/or guided nano granule formation.
" catalytic activity film " refers to the film of one or more chemical reactions of taking place in can the catalytic fuel battery.In some embodiments, the catalytic activity film comprises platinum or platinum alloy.
Brief Description Of Drawings
Fig. 1 has shown the schematic diagram of the detailed structure of catalyst film/carbon nanotube layer/carbon fiber sheet.
The load current that Fig. 2 has shown micro fuel cell is fixed as four kinds of continuous three-way catalyst Ni-Co, Ni-Mo, Ni-V, Co-Mo, Co-V and Mo-V of 40% of each alloy system with the Pt content of negative electrode one side) form the variation that takes place.By being carried out hot pressing, commercially available Pt-Ru commodity electrode (from ElectroChem), Nafion 117 and three layers being deposited on the catalyst on the TORAY carbon fiber paper make micro fuel cell.Each test is carried out on 0.785 square millimeter zone.
Fig. 3 A has shown the load current of micro fuel cell and the function relation figure of the Pt concentration in the different platinum alloy catalyst with Fig. 3 B.Fig. 3 A shows the load current and the Pt of micro fuel cell xV 1-xThe function relation figure of Pt concentration in the alloy catalyst.Relatively the stability of V/Pt-O is confirmed Pt xV 1-xThe oxidation effect of catalyst.The catalyst of target one side and anode one side has all carried out described test.By being carried out hot pressing, PtRu commodity electrode (from ElectroChem), Nafion 117 and three layers being deposited on the Pt-V catalyst on the TORAY carbon paper make micro fuel cell.Each test is carried out on 0.785 square millimeter zone.Fig. 3 B shows the load current and the Pt of micro fuel cell xCo 1-xThe function relation figure of Pt concentration in the alloy catalyst.Relatively the stability of Co/Pt-O is confirmed Pt xCo 1-xThe oxidation effect of catalyst.The catalyst of target one side and anode one side has all carried out described test.By being carried out hot pressing, PtRu commodity electrode (from ElectroChem), Nafion 117 and three layers being deposited on the Pt-V catalyst on the TORAY carbon paper make micro fuel cell.Each test is carried out on 0.785 square millimeter zone.
The load voltage that Fig. 4 has shown micro fuel cell is fixed as four kinds of continuous three-way catalyst Ni-Co of 20%, Ni-V, Co-V of each alloy system and four-way catalyst Ni0.5 (Co continuously with the Pt content of negative electrode one side 1-xV x) 0.5Form the variation that takes place.By being carried out hot pressing, Pt-Ru commodity electrode (from ElectroChem), Nafion 117 and three layers being deposited on the catalyst on the TORAY carbon fiber paper make micro fuel cell.Each test is carried out on 0.785 square millimeter zone.
Fig. 5 has shown the function relation figure between the catalyst layer thickness on the load current of micro fuel cell and negative electrode and the anode both sides.By being carried out hot pressing, Pt-Ru commodity electrode (from ElectroChem), Nafion 117 and three layers being deposited on the catalyst on the TORAY carbon fiber paper make micro fuel cell.Each test is carried out on 0.785 square millimeter zone.
Fig. 6 A and 6B have shown the influence of nanostructure to fuel cell output current.Fig. 6 A has shown the function relation figure of the output current that every milligram of Pt containing in fuel battery voltage and the catalyst is corresponding.Three kinds of samples relatively are three grate firing material batteries of (1) standard assembling, and available from ElectroChem, the Pt catalyst content is 1 milligram/square centimeter, and (2) directly are coated on the Pt on the carbon fiber paper 0.12Co 0.88Film catalyst, (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper 0.12Co 0.88Film catalyst.Fig. 6 B shows the fuel battery power of the every milligram of Pt correspondence that contains in the catalyst and the function relation figure of output current.Three kinds of samples relatively are three grate firing material batteries of (1) standard assembling, and available from ElectroChem, the Pt catalyst content is 1 milligram/square centimeter, and (2) directly are coated on the Pt on the carbon fiber paper 0.12Co 0.88Film catalyst, (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper 0.12Co 0.88Film catalyst.
Fig. 7 A and 7B show the influence of platinum content to fuel cell output power.Fig. 7 A has shown the function relation figure of the output current that every milligram of Pt containing in fuel cell voltage and the catalyst is corresponding.Three kinds of samples relatively are three grate firing material batteries of (1) standard assembling, and available from ElectroChem, the Pt catalyst content is 1 milligram/square centimeter, and (2) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper 0.12Co 0.88Film catalyst and (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper 0.24Co 0.76Film catalyst.Fig. 7 B shows the fuel battery power of the every milligram of Pt correspondence that contains in the catalyst and the function relation figure of output current.Three kinds of samples relatively are three grate firing material batteries of (1) standard assembling, and available from ElectroChem, the Pt catalyst content is 1 milligram/square centimeter, and (2) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper 0.12Co 0.88Film catalyst and (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper 0.24Co 0.76Film catalyst.
Fig. 8 A and 8B have shown the power output of fuel cell.Fig. 8 A shows the function relation figure of the output current that every milligram of Pt containing in fuel battery voltage and the catalyst is corresponding.Three kinds of samples relatively are three grate firing material batteries of (1) standard assembling, and available from ElectroChem, the Pt catalyst content is 1 milligram/square centimeter, and (2) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Ni catalyst 0.12Co 0.88Film catalyst and (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 400  catalyst 0.12Co 0.88Film catalyst.Fig. 8 B shows the fuel battery power of the every milligram of Pt correspondence that contains in the catalyst and the function relation figure of output current.Three kinds of samples relatively are three grate firing material batteries of (1) standard assembling, and available from ElectroChem, the Pt catalyst content is 1 milligram/square centimeter, and (2) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Ni catalyst 0.12Co 0.88Film catalyst and (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 400  Ni catalyst 0.12Co 0.88Film catalyst.
Fig. 9 A and 9B have shown the influence of nanostructure to fuel cell output.Fig. 9 A has shown the function relation figure of the output current that every milligram of Pt containing in fuel battery voltage and the catalyst is corresponding.Three kinds of samples relatively are three grate firing material batteries of (1) standard assembling, and available from ElectroChem, the Pt catalyst content is 1 milligram/square centimeter, and (2) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Co catalyst 0.12Co 0.88Film catalyst and (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Ni catalyst 0.12Co 0.88Film catalyst.Fig. 9 B shows the fuel battery power of the every milligram of Pt correspondence that contains in the catalyst and the function relation figure of output current.Three kinds of samples relatively are that (1) directly is coated on the Pt on the carbon fiber paper 0.12Co 0.88Film catalyst, (2) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Co catalyst 0.12Co 0.88Film catalyst and (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Ni catalyst 0.12Co 0.88Film catalyst.
Figure 10 has illustrated the nano particle (for example, carbon nano-tube) of going up growth at fiber (for example, carbon fiber).Nano particle is coated with continuous substantially catalytic activity film (seeing illustration) partially or completely.
Figure 11 shows the SEM figure of following three kinds of samples: (1) directly is coated on the Pt on the carbon fiber paper 0.12Co 0.88Film catalyst, (2) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Co catalyst 0.12Co 0.88Film catalyst and (3) are coated on the Pt on the carbon nano-tube that is grown directly upon on the carbon fiber paper with 200  Ni catalyst 0.12Co 0.88Film catalyst.
Figure 12 illustrates the structure of three layers of electric conducting material, and wherein each layer has optimized porosity and thickness.
The A-F of Figure 13 shows the carbon nano-tube that is grown directly upon on the carbon fiber (Toray carbon paper) and the SEM figure of the film on the carbon nano-tube.A: by the figure of the SEM under the 45X multiplication factor of the Pt film sample (250 ) of ion beam sputtering on the carbon nano-tube, wherein nanotube is grown directly upon on the carbon fiber paper substrate by chemical vapour deposition (CVD), and has the Ni as catalyst.White portion on the left comer shows the Pt coating.B: by the figure of the SEM under the 300X multiplication factor of the Pt film sample (250 ) of ion beam sputtering on the carbon nano-tube, wherein nanotube is grown directly upon on the carbon fiber paper substrate by chemical vapour deposition (CVD), and has the Ni as catalyst.Cover on each carbon fiber of Toray carbon paper top layer with showing even carbon nanotube among the figure, and the diameter of exposed carbon fiber is increased to about 30-40 micron (as through the CNT coated fibres) from about 10 microns, shows that the thickness of CNT layer on the carbon fiber is about 10 microns.C: by the figure of the SEM under the 3000X multiplication factor of the Pt film sample (250 ) of ion beam sputtering on the carbon nano-tube, wherein nanotube is grown directly upon on the carbon fiber paper substrate by chemical vapour deposition (CVD), and has the Ni as catalyst.Be presented among the figure and form uniform carbon nanotube network on the carbon fiber.D: by the figure of the SEM under the 20000X multiplication factor of the Pt film sample (250 ) of ion beam sputtering on the carbon nano-tube, wherein nanotube is grown directly upon on the carbon fiber paper substrate by chemical vapour deposition (CVD), and has the Ni as catalyst.Be presented among the figure and form uniform carbon nanotube network on the carbon fiber.E: by the figure of the SEM under the 100000X multiplication factor of the Pt film sample (250 ) of ion beam sputtering on the carbon nano-tube, wherein nanotube is grown directly upon on the carbon fiber paper substrate by chemical vapour deposition (CVD), and has the Ni as catalyst.The single-size that shows neat carbon nano-tube among the figure is 100 nanometers.F: by the figure of the SEM under the 200000X multiplication factor of the Pt film sample (250 ) of ion beam sputtering on the carbon nano-tube, wherein nanotube is grown directly upon on the carbon fiber paper substrate by chemical vapour deposition (CVD), and has the Ni as catalyst.Be presented at the continuous Pt film coating of formation on each carbon nano-tube among the figure.
Figure 14 illustrates the advantage of fuel catalyst of the present invention and nano particle.In some embodiments, fuel-cell catalyst can be incorporated into (as described in enforcement mode B) in the porous electrode, thereby has eliminated independent catalyst layer and the little diffusion layer that exists in the conventional construction (as described in enforcement mode A).
Describe in detail
I. fuel-cell catalyst
The present invention relates to for the improved catalyst of fuel cell and the gas of integration-diffusion/electrode/urge Change the exploitation of agent (IGEC). The present invention also provides fuel cell, the combustion that utilizes described improved catalyst The combination of material battery electrode.
In some embodiments, catalyst of the present invention comprises to be coated with and contains catalytically-active metals (example As, platinum, platinum alloy etc.) the nano particle of film of basic continous. Be not subject to concrete theory, according to Letter increases effective active by the film that contains catalytically-active metals or alloy in the nano particle deposition The area on surface can improve the catalytic efficiency of film. Nano particle can partly be coated with substantially Continuous film or covered by this film fully. In typical embodiment, the thickness range of film Be about 1 nanometer to 500 nanometer, preferably be about 2 nanometer to 300 nanometers, be more preferably 5 nanometers To 100 nanometers, be most preferably 10 nanometer to 50 nanometers.
Nano particle can comprise any nano particle in the numerous species. Usually nano particle at least The one dimension size is approximately less than 500 nanometers, more preferably respectively ties up size in two-dimension sizes or the three-dimensional dimension at least Approximately less than 500 nanometers. In some embodiments, the feature of nano particle is that the one dimension size is about at least Less than 100 nanometers or 50 nanometers.
Suitable nano particle include, but not limited to various fullerenes (fullerenes), CNT, The fullerene of Carbon Nanohorn, carbon (and other) nanofiber, nanosphere/powder, quantum dot, metal parcel Deng. Some preferred embodiment in, nano particle is in conjunction with carbon. Therefore, carbon-based nano particle bag Draw together, but be not limited to, CNT, Carbon Nanohorn, carbon nano-fiber, nanosphere/powder etc., especially suitable Share in catalyst of the present invention.
Nano particle can be many possible and any shapes in pattern of the present invention of standing good Looks. Therefore, for example, the present invention considers to use the nanotube of following kind: single wall formula, double-walled, Many wall types, in a zigzag spatially spiral formula nanotube, or spatially spiral, distortion, linear, bending, The mixture of knot, curling, flat and circular nanotube; The nanotube of the thigh of nanotube, distortion, The nanotube of plait shape; The tuftlet of nanotube (for example, in some embodiments, the pipe number approximately less than 10), the middle bundle of nanotube (for example, in some embodiments, the pipe number is in hundreds of), nanometer The big bundle of pipe (for example, in some embodiments, the pipe number is in thousands of); Nanometer frame (nanotorii), Doughnuts (nanocoils), nanometer rods, nano wire, nano horn; Hollow Nano cage (nanocages), fill out The nanocages of filling, multiaspect nanocages, hollow Nano cocoon (nanococoons), filling nanometer cocoon, multiaspect The nanometer cocoon; Thin nanometer sheet (nanoplatelets), thick nanometer sheet, plug-in type nanometer sheet, etc. Various Nano particle (nanostructured) can be assumed to be heterogeneous form. This heterogeneous form includes, but are not limited to Such structure, namely the part in this structure has certain chemical composition, and other of this structure Part has different chemical compositions. An example is many wall types nanotube, wherein the chemistry of different walls Forming each other can be not identical. Heterogeneous form also can comprise the multi-form of nanostructured formed material, Wherein the more than a kind of form in the above-mentioned form is attached in the bigger irregular structure. In addition, In some embodiments, any material in the above-mentioned material can have crack, tomography, branch or Other impurity and/or defective.
The method of making nano particle is well-known to those skilled in the art. Therefore, for example, the U.S. Patent 6451175,6713519,6712864,6709471 and (1999) J.Am.Chem. such as Hafner Soc., 121:9750-9751; Hafner etc. (1999) Scientific Correspondence 398:761-762 Deng in the method for preparing CNT has been described. Similarly, such as (2000) Physical such as Berber Review B, 62 (4): the production of nano horn has been described among the R2291-2294, and United States Patent (USP) for example 6706248, the production of nanofiber described in 6485858, etc.
In catalyst of the present invention, nano particle partly or entirely contained catalytically-active metals or The film of the basic continous of alloy covers. In some embodiments, catalytically-active metals or alloy Comprise platinum (Pt). Suitable alloy includes, but are not limited to: bianry alloy, such as Pt-Cr, Pt-V, Pt-Ta, Pt-Cu, Pt-Ru, Pt-Y etc.; And/or ternary alloy three-partalloy, include but not limited to, Pt-Ru-Os, Pt-Ni-Co, Pt-Cr-C, Pt-Cr-Ce, Pt-Co-Cr, Pt-Fe-Co, Pt-Ru-Ni, Pt-Ga-Cr-Co, Pt-Ga-Cr-Ni, Pt-Co-Cr etc.; And/or quaternary alloy, include but not limited to Pt-Ni-Co-Mn, Pt-Fe-Co-Cu etc.
The platinum content of unit are (for example, the unit are of catalyst) is that practical PEM fuel cell is used One of most important cost standard of product. In some embodiments, to contain Co, Ni, Mo and The binary of the Pt alloy of V, ternary and quaternary composition are optimized, as shown in Figure 2. As shown in Figure 3, Find that vanadium can improve the oxidative resistance of catalyst significantly. Therefore, in some embodiments, thin Film comprise contain platinum (Pt) and vanadium (V) and optional one or more other metals (for example, Co, Ni, Mo, Ta, W, Zr etc.) alloy. In some embodiments, the PtNiCoV alloy is preferred The Pt alloy catalyst system that is used for anode of fuel cell and negative electrode, as shown in Figure 4.
Also the platinum in the platinum alloy system (Pt) concentration has been carried out optimization. Fig. 3 A and 3B demonstration, with The raising of Pt concentration, the output current of fuel cell increases sharply, but closes at Pt-V and Pt-Co Gold in the system all be Pt concentration when reaching about 12% output current reach capacity. Therefore, in some enforcement In the mode, for negative electrode and/or the anode of PEM fuel cell, preferred in the platinum catalyst alloy Platinum concentration all be 12% or less than 12%.
In some embodiments, to comprise general formula be Pt to filmxV yCo zNi wAlloy, wherein x greater than 0.06 and less than 1; Y, z and w are independently greater than 0 and less than 1; And x+y+z+w=1.
In some embodiments, also the thickness to catalyst layer has carried out optimization, contains to reduce platinum Amount. Fig. 5 shows, for catalyst Pt0.12Co 0.88Alloy, when film thickness is about 100 , Electric current output reaches capacity. Therefore, some preferred embodiment in, the moon of PEM fuel cell The thickness of the film Pt alloy catalyst of the utmost point and/or anode is 100  or less than 100 .
In some embodiments, film is not basic continous, but " diversified ", lower Form a plurality of island/islets on the nano particle of face. In some cases, the film of islet Thickness is about 5 dust to 100 dusts, and area is about 1 to 104Square nanometers.
Can film be applied over nano particle by any method in the multiple conventional method. Real at some Execute in the mode, can apply film by simple chemical method. Therefore, for example, in some enforcement side In the formula, can be by direct spraying or nano particle is exposed to contain solvent and the evaporation of thin-film material to remove Desolventizing is with on the film paint nano particle. In some embodiments, film can be by electricity Deposition (for example electroplating) deposits on the nano particle. In some embodiments, the semiconductor by routine Processing method is on the film paint nano particle, for example sputter of these semiconductor processing methods, chemistry Vapour deposition (CVD), molecular beam epitaxy (MBE), plasmaassisted vapour deposition, etc. (referring to, For example, Choudhury (1997) The Handbook of Microlithography, Micromachining, And Microfabrication, Soc.Photo-Optical Instru.Engineer, Bard ﹠ Faulkner (1997) Fundamentals of Microfabrication, etc.).
As noted before, come by the film that basic continous is provided at nano particle (for example nanotube) Improve the catalytic effect of film. For example, Fig. 6 A shows carbon nanotube loaded Pt0.12Co 0.88Catalyst Can be under identical operating voltage the output current of every milligram of Pt be improved an order of magnitude. Fig. 6 B Show carbon nanotube loaded Pt0.12Co 0.88Catalyst can be with the every milli in the whole current work scope The power output of gram Pt improves an order of magnitude. Fig. 7 A and 7B reconfirm, 12% Pt for Carbon nanotube loaded Pt alloy catalyst is enough.
Fig. 8 A and 8B show the carbon nanometer that is subjected to catalyst thickness, growth time and catalyst material control The density of pipe and size can affect catalyst performance. In some embodiments, preferred CNT From several nanometers to 100 nanometers, and has optimum density. Figure 13 is presented at ESEM and amplifies 45 To 200000 times of structures that are coated on the film catalyst on the CNT of observing, wherein carbon nanometers Pipe is grown directly upon on the carbon fiber of Toray carbon paper top layer. Be grown in to even carbon nanotube each fiber On, shown in Figure 13 (b). Shown in c, d and e among Figure 13, the thickness of carbon nanotube layer is about 10 Micron is uniform network structure. F shows that Pt film (catalyst) is on the CNT among Figure 13 Continuous film.
The nano particle that is used for catalyst of the present invention can be various forms, for example, in solution, As dried powder and/or be grown on the porous substrate. In some embodiments, nanoparticle growth Be retained on the porous substrate. In some embodiments, this porous substrate itself is as electrode.
II. the optimization of nanoparticle catalyst (crystal seed)
In some embodiments, the present invention relates to (more preferably be used for the carbon nanometer for nanoparticle growth The optimization of the catalyst pipe growth). Some preferred embodiment in, nano particle (for example receive by carbon Mitron) in the upper growth of carrier (for example, carbon fiber), the film of applied upper basic continous (for example, then The catalytic activity film).
When some nano particle (for example, CNT) is grown, nanoparticle catalyst (" crystal seed ") Often be exposed on the surface (for example, CNT end) of nano particle. Therefore, when film is applied In the time of to the nano particle that comprises described catalyst (crystal seed), catalyst (crystal seed) particle and film forming Material mixes, and can change the catalytic activity of film. Therefore, wish to use suitable nanoparticle growth And can improve or substantially can not cause dysgenic nanometer to the catalytic activity of the film that applies Particulate catalyst materials promotes nanoparticle growth.
Be surprised to find not all nanoparticle catalyst to nanoparticle growth and operation of fuel cells All be useful. Therefore, for example, iron is useful for carbon nano tube growth, but but can disturb The catalytic activity of the film that applies. Some elements, aluminium for example, as if the work to fuel cell does not have Harmful effect is arranged. Some elements or their alloy for nano particle (for example, CNT) growth and Operation of fuel cells all is useful. The seed crystal material of these " the bests " include, but not limited to Co, Ni, V and Mo.
Be surprised to find following listed alloy and be particularly suitable for carbon nano tube growth and operation of fuel cells. They have improved the catalytic property of fuel cell to a great extent.
1.Co 1-xMo x, 0≤x≤0.3 wherein;
2.Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein;
3.Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein;
4.Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein;
5.Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.
6.Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein.
In some particularly preferred execution mode, the catalyst that is used for nanoparticle growth comprises following listed one or more: Co 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
III. electrode-barrier film makes up and manufacture method
In some embodiments, fuel-cell catalyst of the present invention (the partly or entirely nano particle that is covered by basic continuous films) is fabricated onto in electrode/barrier film combination.A kind of typical electrode/barrier film combination comprises: at least one contains first conductive electrode of first fuel-cell catalyst (partly or entirely by the continuous substantially nano particle that catalytic film covered); At least one contains second conductive electrode of second fuel-cell catalyst; With the proton exchange membrane that first conductive electrode and second conductive electrode are separated.
In a more traditional structure (referring to, for example, " A " among Figure 14), catalyst (being coated with the nano particle of film) forms interlayer on electrode or membrane for polymer.In addition, can choose wantonly and have little diffusion layer.Therefore, this structure comprises seven independent layers (two electrodes, two catalyst layers, two little diffusion layers and a PEM).But, but nano particle can with the fiber of air inclusion diffusion electrode (for example, carbon fiber sheet) staggered, fuel-cell catalyst (being coated with the nano particle of film) just can be made with the mode that electrode combines like this, and this is surprised discovery of the present invention and advantage.
In addition, nanoparticle catalyst itself can be used as little diffusion layer, so extra little diffusion layer and nonessential or hope.Therefore, in some embodiments, the present invention considers the gaseous diffusion/electrode/catalyst (IGEC) integrated and the combination of barrier film, and this combination includes only three layers; For example, two IGEC layers, they are separated (for example, referring to, " B " among Fig. 4) by a proton exchange membrane.
Little diffusion layer of this integration and catalyst/carbon layer are easy to make.For example, can make carbon nano-tube (CNT) be grown directly upon on the carbon fiber on the carbon fiber sheet superficial layer (1-5 fibre diameter) (referring to, for example, Figure 10).The diameter of exposed carbon fiber be about 10 microns (referring to, Figure 11,1), and the diameter that is coated with the carbon of CNT is about 50 microns (referring to, Figure 13, B).Like this, the macroscopic void of gas-diffusion electrode is converted into small holes, and the top carbon fiber layer that is coated with CNT can be used as little diffusion layer, improves the dispersion of gas (for example, hydrogen) to catalyst.The platinum or the alloy firm that are coated on the carbon nano-tube top layer can be as having the effective catalyst structure of high surface area.
In another approach, nano particle (for example, CNT, CNH or other nano powder) can be sprayed on the carbon fiber sheet (or other gas-diffusion electrode), then with described film coated on nano-particle layer.As shown in figure 12, middle little diffusion layer can randomly be used between nano particle/catalyst layer and the carbon fiber sheet (gas-diffusion electrode).
In some embodiments, fiber or the palpus crystalline substance of being made by carbon and/or other electric conducting material can be grown on the porous, electrically conductive base material.They can be as the carrier of supported catalyst film.In a preferable methods, carbon nano-tube is directly grown on the commodity carbon fiber paper; To be deposited on the carbon nano-tube as the catalyst film of Pt, Ni, Co, Fe and their alloy by chemical vapour deposition (CVD) then, shown in the schematic diagram of Fig. 1.Also can or brush on carbon fiber paper (gaseous diffusion) electrode carbon nano-tube or other similarly nano-structured electric conducting material spraying.Then, the platinum alloy film catalyst can be deposited on these carbon nanotube layers of direct contact proton exchange membrane (PEM).
In some embodiments, carbon nano-tube or other similarly the nano-structured electric conducting material thin slice that also can be used as and have optimum porosity and preferred thickness (for example, from several nanometers to tens of microns) prepare.Then this thin slice is placed into or is pressed on the carbon fiber paper.Then this film catalyst is deposited on the carbon nanotube pieces of direct contact proton exchange membrane.
Some preferred embodiment in, at first be coated with each carbon nano-particle (for example, carbon nano-tube) with film catalyst.For example, can use plating to make this carbon nano-tube or other the similar nano-structured electric conducting material that has been coated with catalyst.The nano-structured electric conducting material that then these has been coated with catalyst sprays, brushes or be painted on carbon paper electrode or the fuel cell barrier film layer.Perhaps, these nano-structured electric conducting materials that have been coated with catalyst thin slice of also can be used as and having optimum porosity and preferred thickness (from several microns to tens of microns) prepares.Then this thin slice is placed or is pressed on the carbon fiber paper.
Generally speaking, shown in Figure 12 and 14, the preferred structure that each layer has three layers of electric conducting material of best porosity and thickness is the most effective and most economical for operation of fuel cells.For example, top layer is made by the carbon nano-tube that has been coated with the catalytic film catalyst, wherein the diameter of carbon nano-tube to 100 nanometers, has for example high aspect ratio (providing big as far as possible surface to catalytic action) and micron order or nanoscale hole dispersion layer uniformly from several nanometers.Can accurately control the thickness (for example, to tens nanometer pipe layer, because these materials all are very expensive materials) of this layer.In some embodiments, the intermediate layer is made by carbon fiber or powder, and wherein the diameter of fiber or carbon ball is extremely several microns of sub-micron (submicrometer), and bed thickness is about ten microns to tens of microns.Fibre diameter is that the commodity Toray carbon fiber paper that several microns extremely tens of microns, paper thickness are the hundreds of micron is applicable to the application.The aperture and the density of this structure slowly change from the bottom to the top layer.
Material as proton exchange membrane (PEM) is well-known to those skilled in the art.Suitable proton exchange membrane material comprises, but be not limited to, Nafion, silicon dioxide Nafion compound (referring to, for example, Adjemian etc. (2002) J.Electrochem.Soc., 149 (3): A256-A261), be used for the poly phosphazene (inorganic/organic polymer of mixing of high temperature PEMFC, have-the P=N-main chain) (referring to, for example, Fedkin etc. (2002) Materials Letters, 52:192-196; Chalkova etc. (2002) Electrochemical and Solid State Letters, 10:221-223), metal foaming material (referring to, for example, (2002) Fuel Cell Technology News, 4 (9)), poly-(2 of sulfonation, 6-dimethyl-1, the 4-phenylene oxide) (PPO), polystyrene-block-poly-(inferior ethene-random-butylidene)-block＜/I 〉-polystyrene, poly-[(vinyl chloride-altogether-(1-methyl-4-vinyl piperazine, poly-(the 2-vinylpyridine-altogether-styrene), SiO 2-polymer compound proton exchange barrier film, or the like.
V. fuel cell/fuel cells applications
Septum electrode combination of the present invention (septum electrode assembly) can use (assembling) to improve the output of voltage and power in groups, forms fuel cell thus, and this fuel cell can send the power of the application-specific desired level that will use this fuel cell.In battery pile, adjacent single battery (septum electrode assembly) is electrically connected by bipolar plates (BPP) usually, and wherein bipolar plates is arranged between two relative with the face of contact electrolyte membrance in two electrodes faces.These BPP are not have infiltratively to reactant usually, are penetrated into comparative electrode to prevent reactant, take place to mix and runaway chemical reactions.Consider this function, BPP often is called as dividing plate.BPP or dividing plate are made (referring to, for example, United States Patent (USP) 4214969) by metal, particulate carbon and graphite material, impregnated graphite or other molding compounds of being made up of graphite and polymer adhesive usually.Lip-deep flow channel of BPP or groove make fuel can arrive adjacent anode, make oxidant can arrive adjacent negative electrode, and can shift out product and unreacted fuel residue and oxidant residue.These flow channels have reduced the usable area of BPP, because electrical-contact area is only limited to the part on the surface between the passage.
Electrode generally includes the loose structure that is called gas diffusion layers (GDL).GDL provides enough admission passages for fuel and oxidant arrive catalyst layer respectively, and leaves the flow channel that catalyst layer enters adjacent BPP for product outlet is provided.For the ease of the transmission of the quality between flow channel and the GDL hole, the GDL surface area that is exposed to passage is all big as far as possible usually.Therefore, the major part on preferred BPP surface is shared by flow channel, has only small part to stay and is used to electrically contact.But the high contact resistance between BPP and the GDL has limited the minimizing of electrical-contact area.Contact area between the two need be large enough to can avoid under high current density local overheating taking place, and this finally can cause assembly destroyed.
More existing proposals are used for improving electrically contacting between BPP and the GDL, and known to those skilled in the art.For example United States Patent (USP) 4956131 and 6706437 and European patent EP-A0955686, EP-A 0949704, EP-A 0975040, EP-A 0933825, EP-A 1030393 etc. in suitable method has been described.
Fuel cell according to manufacturing of the present invention is the energy that in fact is applicable to any articles for use.These class articles for use include, but not limited to electric motor car, computer, mobile phone and other electronic device, household system etc.Fuel cell is desirable especially, because the pollution that they have shown high-energy transformation efficiency, high power density and almost can disregard.In vehicle such as automobile, a kind of convenient source of hydrogen is the steam reforming of methyl alcohol, because methyl alcohol is stored in the vehicle than hydrogen is easier.
Method described in the literary composition, device and articles for use are illustrative, and nonrestrictive.Use the content described in the literary composition, those skilled in the art can implement other manufacture method etc. routinely.
Embodiment
Following examples are used for illustrating but not the present invention of requirement for restriction right.
Embodiment 1
Handle Pt alloy firm catalyst by multilayer deposition and back diffusion annealing.For having the fixing alloy film of forming, use required the forming of thickness ratio control of calculating by selected atoms of elements amount.For the alloy film that composition continuously changes, in the process of deposition, produce the graded of thickness.Under the representative condition of 10-4 holder and room temperature, use the simple metal target to carry out ion beam sputter depositing.Usually the gross thickness of multilayer is about 100 .The after annealing that carries out for interior diffusion is at about 700 ℃, 10 -8Carried out 12 hours under the vacuum of holder.The commodity in use carbon fiber paper is as the base material of most of composition research.
Improve the surface area of catalyst by being deposited on carbon nano-tube on the carbon fiber paper, little gas diffusion structure is provided.The step of carbon nano-tube is on the carbon fiber of Toray carbon paper:
(1) Ni that deposition 200  are thick on carbon fiber paper is as catalyst;
(2) carbon fiber paper is put into and Ar, H 2And C 2H 4The tube furnace that gas piping connects (6 ' is long, and diameter is 2 ") in;
(3) feed the Ar stream 30 minutes that speed is 100 ml/min, drive away air;
(4) in tube furnace, feed Ar (50 ml/min) and H 2The mixture of (10 ml/min) begins temperature is elevated to 700 ℃ with 20 ℃/minute speed;
(5), the gas stream mixture is adjusted into Ar (15 ml/min), H at 700 ℃ 2(15 ml/min) feeds in the tube furnace, carries out 10 minutes;
(6) make temperature drop to 20 ℃ with 20 ℃/minute speed.
The step that nanotube is sprayed on the carbon is:
Nanotube is ground in the agate ball grinding machine with ethanol.The suspension that is produced is smeared or sprayed on the Toray carbon paper.On the topsheet surface of the nanotube of smearing, deposit Pt by means of electron beam deposition.The catalytic efficiency of measuring reaches the level on the nanotube of growth.
The step of making fuel cell comprises:
(1) drip to nafion solution (5 moles of %) on the carbon paper that is coated with catalyst or on carbon nano-tube/carbon paper, at air drying,
(2) cutting a slice and catalyst sample same size be coated with the ElectroChem carbon electrode of Pt/Ru carbon printing ink as catalyst (Pt: Ru=2: 1, Pt=1 milligram/square centimeter),
(3) normal electrode, barrier film and catalyst sample are put on the hot press with sandwich structure.80 ℃ with the compacting of 1 ton pressure they 10 minutes, form the fuel cell barrier film assembly.
The condition of all fuel cell tests all is; O in anode one side room 2Flow velocity is H in 100 ml/min and negative electrode one side room 2Flow velocity is 100 ml/min.All system sealing secluding airs, and remain on 80 ℃.The load of using a series of resistance (1～4700 ohm) to come the fuel metering battery.The Keithley universal instrument is used for the output voltage and the electric current of control and measuring fuel cell.
Should understand embodiment described in the literary composition and execution mode just for illustrative purposes, those skilled in the art can do various changes or variation in view of the above, and these changes and variation are also included within the scope of the application's spirit and scope and claims.The full content of all publications, patent and the patent application of quoting in the literary composition is in order all to be incorporated into this by reference.

Claims (126)

1. composition, it comprises the conductive fiber that nano particle in a plurality of loads.
2. composition as claimed in claim 1 is characterized in that described conductive fiber is a carbon fiber.
3. composition as claimed in claim 1 is characterized in that, described nano particle is selected from down group: nanotube, nanofiber, nanometer are prominent, nano powder, nanosphere and quantum dot.
4. composition as claimed in claim 1 is characterized in that described nano particle is a carbon nano-tube.
5. composition as claimed in claim 1 is characterized in that, described a plurality of conductive fibers comprise porous electrode.
6. composition as claimed in claim 2 is characterized in that described carbon fiber comprises porous electrode.
7. composition as claimed in claim 2 is characterized in that, described a plurality of carbon fibers comprise carbon paper or carbon cloth or carbon polymers impregnated.
8. composition as claimed in claim 1 is characterized in that, described a plurality of conductive fibers comprise the porous metals sheet.
9. composition as claimed in claim 4 is characterized in that, described carbon nano-tube forms crystal seed with one or more catalyst, and described catalyst comprises one or more materials that is selected from down group: Co, Ni, V, Cr, Pt, Ru, Mo, W, Ta and Zr.
10. composition as claimed in claim 4 is characterized in that, described carbon nano-tube forms crystal seed: Fe with the catalyst that one or more are selected from down group xNi yCo 1-x-y, 0≤x≤1,0≤y≤1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.
11. composition as claimed in claim 4 is characterized in that, described carbon nano-tube forms crystal seed: Co with the catalyst that one or more are selected from down group 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
12. composition as claimed in claim 4 is characterized in that, described nano particle is a length less than 50 microns, diameter approximately less than the nanotube of 100 nanometers.
13. composition as claimed in claim 4 is characterized in that, described nano particle is the nanotube that diameter is about 1 nanometer to 100 nanometer.
14., it is characterized in that described nano particle is coated with the basic continuous films that comprises platinum alloy as claim 1 or 4 described compositions.
15. composition as claimed in claim 14 is characterized in that, described film portion ground covers described nano particle.
16. composition as claimed in claim 14 is characterized in that, described nano particle is coated with described film fully.
17. composition as claimed in claim 14 is characterized in that, the thickness of described film is about 1 dust to 1000 dust.
18. composition as claimed in claim 17 is characterized in that, the thickness of described film is about 5 dust to 500 dusts.
19., it is characterized in that described nano particle is coated with the discrete film that comprises platinum alloy as claim 1 or 4 described compositions.
20. composition as claimed in claim 19 is characterized in that, described film comprises that thickness is about 5 dust to 100 dusts, area is about 1 to 10 4The island of square nanometers.
21. composition as claimed in claim 17 is characterized in that, the thickness of described film is about 5 dust to 100 dusts.
22. composition as claimed in claim 21 is characterized in that, described film comprises a kind of alloy, and described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co, Ni, Mo, Ta, W and Zr.
23. composition as claimed in claim 22 is characterized in that, described film comprises a kind of alloy, and described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co and Ni.
24. composition as claimed in claim 22 is characterized in that, described platinum accounts for 50% (mol ratio or atomic percentage) at most in described alloy.
25. composition as claimed in claim 22 is characterized in that, described platinum accounts for 12% (mol ratio or atomic percentage) at most in described alloy.
26. composition as claimed in claim 22 is characterized in that, described alloy comprises platinum, vanadium, nickel and cobalt.
27. composition as claimed in claim 22 is characterized in that, it is Pt that described film comprises general formula xV yCo zNi wAlloy, wherein:
X is greater than 0.06 and less than 1;
Y, z and w are respectively greater than 0 and less than 1;
And x+y+z+w=1.
28. composition as claimed in claim 27 is characterized in that, x is 0.12.
29. composition as claimed in claim 27 is characterized in that, x is 0.12, and y is 0.07, and z is 0.56, and w is 0.25.
30. a fuel-cell catalyst that comprises a plurality of nano particles, described nano particle are coated with the basic continuous films that comprises platinum or platinum alloy.
31. fuel-cell catalyst as claimed in claim 30 is characterized in that, described film portion ground covers described nano particle.
32. fuel-cell catalyst as claimed in claim 30 is characterized in that, described nano particle is coated with described film fully.
33. fuel-cell catalyst as claimed in claim 30 is characterized in that, the thickness of described film is about 1 dust to 1000 dust.
34. fuel-cell catalyst as claimed in claim 33 is characterized in that, the thickness of described film is about 5 dust to 500 dusts.
35. fuel-cell catalyst as claimed in claim 33 is characterized in that, the thickness of described film is about 5 dust to 100 dusts.
36. fuel-cell catalyst as claimed in claim 30 is characterized in that, described film comprises a kind of alloy, and described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co, Ni, Mo, Ta, W and Zr.
37. fuel-cell catalyst as claimed in claim 36 is characterized in that, described film comprises a kind of alloy, and described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co and Ni.
38. fuel-cell catalyst as claimed in claim 36 is characterized in that, described platinum accounts for 50% (mol ratio or atomic percentage) at most in described alloy.
39. fuel-cell catalyst as claimed in claim 36 is characterized in that, described platinum accounts for 12% (mol ratio or atomic percentage) at most in described alloy.
40. fuel-cell catalyst as claimed in claim 39 is characterized in that, described alloy contains platinum, vanadium, nickel and cobalt.
41. fuel-cell catalyst as claimed in claim 36 is characterized in that, it is Pt that described film comprises general formula xV yCo zNi wAlloy, wherein:
X is greater than 0.06 and less than 1;
Y, z and w are respectively greater than 0 and less than 1;
And x+y+z+w=1.
42. fuel-cell catalyst as claimed in claim 41 is characterized in that, x is 0.12.
43. fuel-cell catalyst as claimed in claim 41 is characterized in that, x is 0.12, and y is 0.07, and z is 0.56, and w is 0.25.
44. fuel-cell catalyst as claimed in claim 30 is characterized in that, described nano particle adheres to or is attached in the base material.
45. fuel-cell catalyst as claimed in claim 44 is characterized in that, described nano particle adheres to or is attached in the porous carbon base material.
46. fuel-cell catalyst as claimed in claim 44 is characterized in that, described nano particle adheres to or is attached in the porous, electrically conductive base material.
47. fuel-cell catalyst as claimed in claim 44 is characterized in that, described nano particle is electrically connected with electrode.
48. fuel-cell catalyst as claimed in claim 44 is characterized in that, described nano particle is attached on the polymeric substrate.
49. fuel-cell catalyst as claimed in claim 44 is characterized in that, described nano particle is a carbon nano-tube, and described nanotube is attached to contacting on the carbon fiber or with carbon fiber.
50. fuel-cell catalyst as claimed in claim 30 is characterized in that, described nano particle is selected from down group: nanotube, nanofiber, nanometer are prominent, nano powder, nanosphere and quantum dot.
51. as require 30 described fuel-cell catalysts, it is characterized in that described nano particle is a carbon nano-tube.
52. composition as claimed in claim 30 is characterized in that, described carbon nano-tube forms crystal seed: Fe with the catalyst that one or more are selected from down group xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.
53. composition as claimed in claim 30 is characterized in that, described carbon nano-tube forms crystal seed: Co with the catalyst that one or more are selected from down group 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
54. fuel-cell catalyst as claimed in claim 51 is characterized in that, described nano particle be length approximately less than 200 microns, width approximately less than the nanotube of 100 nanometers.
55. fuel-cell catalyst as claimed in claim 51 is characterized in that, described nano particle is the nanotube that diameter is about 10 nanometer to 100 nanometers.
56. electrode-barrier film combination, it comprises:
At least one comprises first conductive electrode of first fuel-cell catalyst;
At least one comprises second conductive electrode of second fuel-cell catalyst;
The proton exchange membrane that separates first conductive electrode and second conductive electrode;
Described first fuel-cell catalyst and second fuel-cell catalyst are independently selected from as each described catalyst in the claim 30 to 55.
57. electrode diaphragm combination as claimed in claim 56 is characterized in that described first fuel-cell catalyst is different materials with described second fuel-cell catalyst.
58. electrode diaphragm combination as claimed in claim 56 is characterized in that the thickness of described proton exchange membrane is about 2 microns to 100 microns.
59. electrode diaphragm combination as claimed in claim 56 is characterized in that described proton exchange membrane comprises the material that is selected from down group: (PPO) and the SiO 2-polymer compound of Nafion, silicon dioxide Nafion compound, poly phosphazene, sulfonation.
60. electrode diaphragm combination as claimed in claim 56 is characterized in that described first conductive electrode and described first fuel-cell catalyst form interlayer.
61. electrode diaphragm combination as claimed in claim 60 is characterized in that described first conductive layer and first fuel-cell catalyst also are included in the little diffusion layer between described electrode and the described catalyst.
62. electrode diaphragm combination as claimed in claim 56 is characterized in that described first conductive electrode and first fuel-cell catalyst form the individual layer of integrating.
63. electrode diaphragm combination as claimed in claim 62 is characterized in that described first fuel-cell catalyst is also as little diffusion layer.
64. electrode diaphragm combination as claimed in claim 62 is characterized in that described second conductive electrode and second fuel-cell catalyst form the individual layer of integrating.
65., it is characterized in that described second fuel-cell catalyst is also as little diffusion layer as the described electrode diaphragm combination of claim 64.
66. a fuel cell pack, it comprises the electrode diaphragm combination of a plurality of electrical connections, and described electrode diaphragm combination comprises:
At least one comprises first conductive electrode of first fuel-cell catalyst;
At least one comprises second conductive electrode of second fuel-cell catalyst;
The proton exchange membrane that separates first conductive electrode and second conductive electrode;
Described first fuel-cell catalyst and second fuel-cell catalyst are independently selected from as each described catalyst in the claim 30 to 54.
67. an electric device, it comprises as the described fuel cell pack of claim 66.
68., it is characterized in that described device is a haulage vehicle as the described electric device of claim 67.
69. a battery pack substitute is characterized in that, described battery pack substitute comprises the shell that holds as the described fuel cell pack of claim 66, and wherein said shell is provided for the positive terminal and the negative pole end of the device of contact need electric power.
70., it is characterized in that described battery pack substitute is given house, mobile phone, illuminator, computer and/or utensil power supply as the described battery pack substitute of claim 69.
71. a method of making fuel catalyst, described method comprises:
A plurality of nano particles are provided;
Deposition comprises the basic continuous films of platinum or platinum alloy on described nano particle.
72. as the described method of claim 71, it is characterized in that described deposition is undertaken by the method that is selected from down group: sputtering sedimentation, chemical vapor deposition (CVD), ald (ALD), molecular beam epitaxy (MBE), laser treatment, the auxiliary vapour deposition of plasma, electron-beam evaporation, plating and chemical plating.
73. as the described method of claim 71, it is characterized in that, described deposition is to realize on the porous electrode base material by the continuous integrated approach that carries out in the following order: sputter, evaporation, plating, ALD or CVD deposit nanometric particles growth catalyst film, CVD, plasma assisted CVD or laser treatment deposit nanometric particles then, sputter then, evaporation, plating, ALD or CVD deposited fuel cell catalyst film.
74., it is characterized in that described film portion ground covers nano particle as the described method of claim 71.
75., it is characterized in that described nano particle is coated with described film fully as the described method of claim 71.
76., it is characterized in that the thickness of described film is about 1 dust to 500 dust as the described method of claim 71.
77., it is characterized in that the thickness of described film is about 5 dust to 100 dusts as the described method of claim 76.
78., it is characterized in that described film comprises a kind of alloy as the described method of claim 71, described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co, Ni, Mo, Ta, W and Zr.
79., it is characterized in that described film comprises a kind of alloy as the described method of claim 78, described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co and Ni.
80., it is characterized in that described platinum accounts for 12% at most as the described method of claim 78 in described alloy.
81., it is characterized in that described alloy contains platinum, vanadium, nickel and cobalt as the described method of claim 80.
82., it is characterized in that it is Pt that described film comprises general formula as the described method of claim 78 xV yCo zNi wAlloy, wherein:
X is greater than 0.06 and less than 1;
Y, z and w are respectively greater than 0 and less than 1;
And x+y+z+w=1.
83., it is characterized in that x is 0.12 as the described method of claim 82.
84., it is characterized in that x is 0.12 as the described method of claim 82, y is 0.07, z is 0.56, and w is 0.25.
85., it is characterized in that described nano particle is attached on the base material as the described method of claim 71.
86., it is characterized in that described nano particle is attached on the porous carbon base material as the described method of claim 85.
87., it is characterized in that described nano particle is attached on the porous electrode as the described method of claim 85.
88., it is characterized in that described nano particle is electrically connected with porous electrode as the described method of claim 85.
89., it is characterized in that described nano particle is attached on the polymer dielectric film base material as the described method of claim 85.
90., it is characterized in that described nano particle is selected from down group as the described method of claim 71: nanotube, nanofiber, nanometer are prominent, nano powder, nanosphere and quantum dot.
91., it is characterized in that described nano particle is a carbon nano-tube as the described method of claim 71.
92. as the described method of claim 91, it is characterized in that, described nano particle be length approximately less than 50 microns, width approximately less than the nanotube of 100 nanometers.
93., it is characterized in that described nano particle is the nanotube that diameter is about 50 nanometer to 100 nanometers as the described fuel-cell catalyst of claim 92.
94. a method for preparing fuel cell component, described method comprises:
A plurality of fibers and/or porous electrode material are provided;
Deposit nanometric particles catalyst on described a plurality of fibers and/or porous electrode material;
Use described nanoparticle catalyst on described a plurality of fibers and/or porous electrode material, to form nano particle;
Form the catalytic active layer that comprises basic continuous film on described nano particle, comprise the fuel cell component that the fiber of nano particle in a plurality of loads thereby form, wherein said nano particle partly or entirely is coated with the catalytic activity film.
95., it is characterized in that described a plurality of fibers comprise a plurality of carbon fibers as the described method of claim 94.
96., it is characterized in that described a plurality of carbon fibers comprise porous electrode as the described method of claim 95.
97., it is characterized in that described a plurality of fibers comprise carbon fiber paper as the described method of claim 95.
98., it is characterized in that described nanoparticle catalyst is a carbon nano-tube catalyst as the described method of claim 94, described nano particle is a carbon nano-tube.
99., it is characterized in that described nano particle forms by the method that is selected from down group: chemical vapor deposition (CVD), plasma assisted CVD, sputter, laser treatment and ald (ALD) as the described method of claim 98.
100. as the described method of claim 94, it is characterized in that described deposit nanometric particles catalyst comprises that the method by being selected from down group deposits described catalyst on described fiber: sputtering sedimentation, chemical vapor deposition (CVD), ald (ALD), molecular beam epitaxy (MBE), the auxiliary vapour deposition of plasma, electron-beam evaporation, plating and chemical plating and ald (ALD).
101., it is characterized in that described catalyst is the catalyst that is selected from down group: Fe as the described method of claim 98 xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.
102., it is characterized in that described catalyst is the catalyst that is selected from down group: Co as the described method of claim 98 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
103., it is characterized in that the length of described nanotube is less than 50 microns as the described method of claim 98, width is approximately less than 100 nanometers.
104., it is characterized in that the diameter of described nanotube is about 50 nanometer to 100 nanometers as the described method of claim 98.
105., it is characterized in that described nano particle is coated with the basic continuous films that comprises platinum or platinum alloy as the described method of claim 98.
106., it is characterized in that described film portion ground covers described nano particle as the described method of claim 105.
107., it is characterized in that described nano particle is coated with described film fully as the described method of claim 105.
108., it is characterized in that the thickness of described film is about 1 dust to 1000 dust as the described method of claim 105.
109., it is characterized in that the thickness of described film is about 5 dust to 500 dusts as the described method of claim 107.
110., it is characterized in that the thickness of described film is about 5 dust to 100 dusts as the described method of claim 107.
111., it is characterized in that described film comprises a kind of alloy as the described method of claim 110, described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co, Ni, Mo, Ta, W and Zr.
112., it is characterized in that described film comprises a kind of alloy as the described method of claim 111, described alloy contains platinum (Pt), vanadium (V) and one or more are selected from down the metal of group: Co and Ni.
113., it is characterized in that described platinum accounts for 50% (mol ratio or atomic percentage) at most as the described method of claim 111 in described alloy.
114., it is characterized in that described platinum accounts for 12% (mol ratio or atomic percentage) at most as the described method of claim 111 in described alloy.
115., it is characterized in that described alloy contains platinum, vanadium, nickel and cobalt as the described method of claim 111.
116., it is characterized in that it is Pt that described film comprises general formula as the described method of claim 111 xV yCo zNi wAlloy, wherein:
X is greater than 0.06 and less than 1;
Y, z and w are respectively greater than 0 and less than 1;
And x+y+z+w=1.
117., it is characterized in that x is 0.12 as the described method of claim 116.
118., it is characterized in that x is 0.12 as the described method of claim 116, y is 0.07, z is 0.56, and w is 0.25.
119., it is characterized in that as the described method of claim 94:
Describedly provide a plurality of fibers and/or porous electrode material to comprise carbon fiber paper or carbon cloth or porous metals electrode are provided;
Described deposit nanometric particles catalyst comprises by chemical vapour deposition (CVD) or physical vaporous deposition and deposits described catalyst;
Described formation nano particle comprises the formation carbon nano-tube;
Described formation catalytic active layer comprises that deposition contains the basic continuous films of platinum or platinum alloy.
120. a manufacturing is used for the method for the carbon nano-tube of fuel cell, described method comprises:
Provide and be selected from following nanotube growth catalyst: Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein;
On described catalyst, form carbon nano-tube.
121., it is characterized in that described catalyst is the catalyst that is selected from down group: Co as the described method of claim 120 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
122., it is characterized in that described formation is undertaken by being selected from following method: chemical vapor deposition (CVD), sputter, laser treatment and ald (ALD) as the described method of claim 120.
123. a carbon nano-tube, described nanotube comprise the nanotube growth catalyst that is selected from down group: Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.
124., it is characterized in that described catalyst is the catalyst that is selected from down group: Co as the described carbon nano-tube of claim 123 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
125. a catalyst that is used for fuel cell with carbon nano tube growth, described catalyst is the catalyst that is selected from down group: Fe xNi yCo 1-x-y, 0＜x＜1,0＜y＜1 wherein; Co 1-xMo x, 0≤x≤0.3 wherein; Co 1-x-yNi xMo y, 0.1≤x≤0.7,0≤y≤0.3 wherein; Co 1-x-y-zNi xV yCr z, 0≤x≤0.7,0≤y≤0.2,0≤z≤0.2 wherein; Ni 1-x-yMo xAl y, 0≤x≤0.2,0≤y≤0.2 wherein; Co 1-x-yNi xAl y, 0≤x≤0.7,0≤y≤0.2 wherein.
126., it is characterized in that described catalyst is the catalyst that is selected from down group: Co as the described catalyst of claim 125 8.8Mo 1.2, Co 2.2Ni 5.6Mo 2.2, Co 5.7Ni 2.1V 1.1Cr 1.1, Ni 8.0Mo 1.0Al 1.0And Co 6.4Ni 2.4Al 1.2
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