US20090117437A1 - Membrane electrode assembly and method for making the same - Google Patents

Membrane electrode assembly and method for making the same Download PDF

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Publication number
US20090117437A1
US20090117437A1 US12/006,336 US633607A US2009117437A1 US 20090117437 A1 US20090117437 A1 US 20090117437A1 US 633607 A US633607 A US 633607A US 2009117437 A1 US2009117437 A1 US 2009117437A1
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nanotube film
carbon
carbon nanotube
carbon nanotubes
electrode assembly
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US12/006,336
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Chang-Hong Liu
Shou-Shan Fan
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Tsinghua University
Hon Hai Precision Industry Co Ltd
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Tsinghua University
Hon Hai Precision Industry Co Ltd
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Assigned to TSINGHUA UNIVERSITY, HON HAI PRECISION INDUSTRY CO., LTD. reassignment TSINGHUA UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FAN, SHOU-SHAN, LIU, CHANG-HONG
Publication of US20090117437A1 publication Critical patent/US20090117437A1/en
Priority to US14/145,006 priority Critical patent/US9698442B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor

Definitions

  • the invention generally relates to membrane electrode assembly and method for making the same and, particularly, to a carbon nanotube based membrane electrode assembly of a fuel cell and method for making the same.
  • Fuel cells can generally be classified into alkaline, solid oxide, and proton exchange membrane fuel cells.
  • the proton exchange membrane fuel cell has received more attention and has developed rapidly in recent years.
  • the proton exchange membrane fuel cell includes a number of separated fuel cell work units.
  • Each work unit includes a fuel cell membrane electrode assembly (MEA), flow field plates (FFP), current collector plates (CCP), as well as related support equipments, such as blowers, valves, and pipelines.
  • MEA fuel cell membrane electrode assembly
  • FFP flow field plates
  • CCP current collector plates
  • the MEA generally includes a proton exchange membrane and two electrodes separately disposed on two opposite surfaces of the proton exchange membrane. Further, each electrode includes a catalyst layer and a gas diffusion layer. The catalyst layer is configured for being sandwiched between the gas diffusion layer and the proton exchange membrane.
  • the material of the proton exchange membrane is selected from the group consisting of perfluorosulfonic acid, polystyrene sulfonic acid, polystyrene trifluoroacetic acid, phenol formaldehyde resin acid, and hydrocarbons.
  • the catalyst layer includes catalyst materials and carriers.
  • the catalyst materials are selected from the group consisting of metal particles, such as platinum particles, gold particles, and ruthenium particles.
  • the carriers are generally carbon particles, such as graphite, carbon black, carbon fiber or carbon nanotubes.
  • the gas diffusion layer is constituted of treated carbon cloth and carbon paper.
  • the gas diffusion layer of MEA is mainly formed by a carbon fiber paper.
  • a process of making the carbon fiber paper is by the steps of: mixing carbon fibers, wood pulp, and cellulose fibers; using the mixture to obtain a paper pulp; and then forming the carbon fiber paper from the paper pulp.
  • the process of making the carbon fiber paper has the following disadvantages: Firstly, the carbon fibers in the carbon fiber paper are not uniformly dispersed, thereby the gaps therein are uneven resulting in the carbon fibers having a small specific surface area. Thus, the structure restricts the gas diffusion layer to uniformly diffuse the gases, which is needed for the MEA.
  • the carbon fiber paper has high electrical resistance, thus, restricting the transfer of electrons between the gas diffusion layer and the external electrical circuit, thereby reducing the reaction activity of the MEA.
  • the carbon fiber paper has poor tensile strength, and is difficult to process.
  • a membrane electrode assembly includes a proton exchange membrane and two electrodes.
  • the proton exchange membrane includes two opposite surfaces.
  • the two electrodes are separately disposed on the opposite surfaces of the proton exchange membrane.
  • each electrode includes a catalyst layer and a gas diffusion layer.
  • the catalyst layer is configured for being sandwiched between the gas diffusion layer and the proton exchange membrane.
  • the gas diffusion layer includes a carbon nanotube film.
  • the carbon nanotube film includes a plurality of carbon nanotubes entangled with each other. And a method for making the membrane electrode assembly is also included
  • FIG. 1 is a schematic view of a membrane electrode assembly, in accordance with the present embodiment.
  • FIG. 2 is a flow chart of a method for making the membrane electrode assembly shown in FIG. 1 .
  • FIG. 3 shows a Scanning Electron Microscope (SEM) image of a flocculated structure of carbon nanotubes formed by the method of FIG. 2 .
  • FIG. 4 shows a Scanning Electron Microscope (SEM) image of a carbon nanotube film formed by the method of FIG. 2 wherein the carbon nanotube film has a predetermined shape.
  • SEM Scanning Electron Microscope
  • FIG. 5 shows a Scanning Electron Microscope (SEM) image of a carbon nanotube film formed by the method of FIG. 2 wherein the carbon nanotube film has been folded.
  • SEM Scanning Electron Microscope
  • FIG. 6 is a schematic view of a fuel cell in accordance with the present embodiment.
  • a membrane electrode assembly 10 is provided in the present embodiment.
  • the membrane electrode assembly 10 includes a proton exchange membrane 12 and two electrodes 14 .
  • the proton exchange membrane 12 includes two opposite surfaces.
  • the two electrodes 14 are separately disposed on the two opposite surfaces of the proton exchange membrane 12 .
  • each of the electrodes 14 includes a catalyst layer 18 and a gas diffusion layer 16 .
  • the catalyst layer 18 is configured for being sandwiched between the gas diffusion layer 16 and the proton exchange membrane 12 .
  • the gas diffusion layer 16 includes a carbon nanotube film.
  • the carbon nanotube film includes a plurality of carbon nanotubes tangled with each other. The adjacent carbon nanotubes are combined and entangled by van der Waals attractive force, thereby forming a network structure/microporous structure. Further, the carbon nanotubes in the carbon nanotube film are isotropic, uniformly dispersed, and disorderly arranged. Due to the carbon nanotube film having a plurality of carbon nanotubes entangled with each other and the microporous structure, the carbon nanotube film has good tensile strength, thereby having a free-standing structure. It is understood that the carbon nanotube film is very microporous. Sizes of the micropores are less of 100 micrometers. Length and width of the carbon nanotube film are not limited. A thickness of the carbon nanotube film is in an approximate range from 1 micrometer to 2 millimeters.
  • the catalyst materials includes metal particles and carbon particles.
  • the metal particles are selected from the group consisting of platinum particles, gold particles, and ruthenium particles.
  • the carbon particles are selected from the group consisting of graphite, carbon black, carbon fiber, and carbon nanotubes. Quite suitably, the metal particles are platinum; and the carbon particles are carbon nanotubes.
  • the metal particles are dispersed in the carbon particles, thereby forming the catalyst layer 18 .
  • the loading of the metal particles is less of 0.5 mg/cm 2 (milligram per square centimeter).
  • the material of the proton exchange membrane 12 is selected from the group consisting of perfluorosulfonic acid, polystyrene sulfonic acid, polystyrene trifluoroacetic acid, phenol-formaldehyde resin acid, and hydrocarbons.
  • a method for making the above-described membrane electrode assembly 10 are provided in the present embodiment.
  • the method includes the steps of: (a) fabricating a carbon nanotube film to act as a gas diffusion layer; (b) forming a catalyst layer on the carbon nanotube film to obtain an electrode; and (c) providing a proton exchange membrane, and disposing two of the electrodes on opposite surfaces of the proton exchange membrane respectively, thereby forming the membrane electrode assembly.
  • the carbon nanotube film is formed by the substeps of: (a1) providing a raw material of carbon nanotubes; (a2) adding the raw material of carbon nanotubes to a solvent to get a floccule structure; and (a3) separating the floccule structure from the solvent, and shaping/molding the separated floccule structure to obtain a carbon nanotube film.
  • a raw material of carbon nanotubes is an array of carbon nanotubes, quite suitably, a super-aligned array of carbon nanotubes.
  • the array of carbon nanotubes contains a plurality of carbon nanotubes, which are selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
  • the given super-aligned array of carbon nanotubes can be formed by the steps of: (a11) providing a substantially flat and smooth substrate; (a12) forming a catalyst layer on the substrate; (a13) annealing the substrate with the catalyst layer in air at a temperature in the approximate range from 700° C. to 900° C.
  • the substrate can, beneficially, be a P-type silicon wafer, an N-type silicon wafer, or a silicon wafer with a film of silicon dioxide thereon.
  • a 4-inch P-type silicon wafer is used as the substrate.
  • the catalyst can, advantageously, be made of iron (Fe), cobalt (Co), nickel (Ni), or any alloy thereof.
  • the protective gas can, beneficially, be made up of at least one of nitrogen (N 2 ), ammonia (NH 3 ), and a noble gas.
  • the carbon source gas can be a hydrocarbon gas, such as ethylene (C 2 H 4 ), methane (CH 4 ), acetylene (C 2 H 2 ), ethane (C 2 H 6 ), or any combination thereof.
  • the super-aligned array of carbon nanotubes can, opportunely, have a height more than 100 microns and include a plurality of carbon nanotubes parallel to each other and approximately perpendicular to the substrate. Because the length of the carbon nanotubes is very long, portions of the carbon nanotubes are bundled together. Moreover, the super-aligned array of carbon nanotubes formed under the above conditions is essentially free of impurities such as carbonaceous or residual catalyst particles. The carbon nanotubes in the super-aligned array are closely packed together by the van der Waals attractive force.
  • step (a16) the array of carbon nanotubes is scraped from the substrate by a knife or other similar devices to obtain the raw material of carbon nanotubes.
  • a raw material is, to a certain degree, able to maintain the bundled state of the carbon nanotubes.
  • the solvent is selected from the group consisting of water and volatile organic solvent.
  • a process of flocculating is executed to get the floccule structure.
  • the process of flocculating is selected from the group consisting of ultrasonic dispersion and high-strength agitating/vibrating. Quite usefully, in this embodiment ultrasonic dispersion is used to flocculate the solvent containing the carbon nanotubes for about 10 ⁇ 30 minutes.
  • the flocculated and bundled carbon nanotubes form a network structure (i.e., floccule structure).
  • step (a3) the process of separating the floccule structure from the solvent includes the substeps of: (a31) pouring the solvent containing the floccule structure through a filter into a funnel; and (a32) drying the floccule structure on the filter to obtain the separated floccule structure of carbon nanotubes.
  • step (a32) a time of drying can be selected according to practical needs.
  • the floccule structure of carbon nanotubes on the filter is bundled together, so as to form an irregular flocculate structure.
  • step (a3) the process of shaping/molding includes the substeps of: (a33) putting the separated floccule structure into a container (not shown), and spreading the floccule structure to form a predetermined structure; (a34) pressing the spread floccule structure with a certain pressure to yield a desirable shape; and (a35) drying the spread floccule structure to remove the residual solvent or volatilizing the residual solvent to form a carbon nanotube film.
  • the size of the spread floccule structure is, advantageously, used to control a thickness and a surface density of the carbon nanotube film. As such, the larger the area of a given amount of the floccule structure is spread over, the less the thickness and density of the carbon nanotube film.
  • the carbon nanotube film is, advantageously, easy to be folded and/or bent into arbitrary shapes without rupture.
  • the thickness of the carbon nanotube film is in the approximate range from 1 micrometer to 2 millimeters, and the width of the carbon nanotube film is in the approximate range from 1 millimeter to 10 centimeters.
  • the step (a3) can be accomplished by a process of pumping filtration to obtain the carbon nanotube film.
  • the process of pumping filtration includes the substeps of: (a31′) providing a microporous membrane and an air-pumping funnel; (a32′) filtering the solvent containing the floccule structure of carbon nanotubes through the microporous membrane into the air-pumping funnel; and (a33′) air-pumping and drying the floccule structure of carbon nanotubes captured on the microporous membrane.
  • the microporous membrane has a smooth surface. And the diameters of micropores in the membrane are about 0.22 microns.
  • the pumping filtration can exert air pressure on the floccule structure, thus, forming a uniform carbon nanotube film.
  • the carbon nanotube film can, beneficially, be easily separated from the membrane.
  • the carbon nanotube film produced by the method has the following virtues. Firstly, through flocculating, the carbon nanotubes are bundled together by van der Walls attractive force to form a network structure/floccule structure. Thus, the carbon nanotube film is very durable. Secondly, the carbon nanotube film is very simply and efficiently produced by the method. A result of the production process of the method, is that thickness and surface density of the carbon nanotube film are controllable.
  • the carbon nanotube film has good tensile strength.
  • the carbon nanotube film obtained in the present embodiment is folded without rapture. As such, the carbon nanotube film is easy to process, and can, beneficially be folded in most any desired shape.
  • the carbon nanotube film can, beneficially, be cut into any desired shape and size. As such, it is easily applied to use in a fuel cell, especially, in a micro-type of fuel cell acting as a gas diffusion layer.
  • the catalyst layer 18 is formed by the substeps of: (b1) putting metal particles and carbon particles into a dispersion solution; (b2) adding water and a surface active agent to the dispersion solution to obtain a catalyst slurry; (b3) coating the catalyst slurry on the carbon nanotube film and drying the catalyst slurry, thereby forming the catalyst layer on the carbon nanotube film to obtain the electrode.
  • the metal particles are selected from the group consisting of platinum particles, gold particles and ruthenium particles.
  • the carbon particles are selected from the group consisting of graphite, carbon black, carbon fibers, and carbon nanotubes.
  • the metal particles load on surfaces of the carbon particles. Further, loading of the metal particles is less of 0.5 mg/cm 2 .
  • the carbon particles have the properties of high conductivity, a high specific surface area, and good corrosion resistance.
  • a ball mill refiner is used to mill the carbon particles.
  • CHF 1000 resin is dissolved in dimethyl acetamide to form the dispersion solution. A mass percent of the CHF 1000 resin in the dispersion solution is about 5%.
  • step (b2) the surface active agent is used to restrain agglomeration of the carbon particles.
  • isopropanol is used as the surface active agent.
  • step (b3) a process of coating is executed by a spraying method, an immersing method, or a screen printing method.
  • the above-described methods can, opportunely, ensure that the catalyst slurry is uniformly and densely coated on the carbon nanotube film.
  • the drying method is executed at a low temperature.
  • the drying process is selected from the group consisting of an oven drying method and a sintering method.
  • step (c) the two electrodes 14 are attached on the two opposite surfaces of the proton exchange membrane 12 by a heat pressing process. Further, the catalyst layer 18 is configured for being sandwiched between the gas diffusion layer 16 and the proton exchange membrane 12 .
  • the material of the proton exchange membrane 12 is selected from the group consisting of perfluorosulfonic acid, polystyrene sulfonic acid, polystyrene trifluoroacetic acid, phenol formaldehyde resin acid, and hydrocarbons.
  • the fuel cell 600 includes a membrane electrode assembly (MEA) 618 , two flow field plates (FFP) 610 , two current collector plates (CCP) 612 , as well as related support equipment 614 .
  • the MEA 618 includes a proton exchange membrane 602 and two electrodes 604 separately disposed on two opposite surfaces of the proton exchange membrane 602 .
  • each electrode includes a catalyst layer 608 and a gas diffusion layer 606 .
  • the catalyst layer 608 is configured for being sandwiched between the gas diffusion layer 606 and the proton exchange membrane 602 .
  • the proton exchange membrane 602 is selected from the group consisting of perfluorosulfonic acid, polystyrene sulfonic acid, polystyrene trifluoroacetic acid, phenol-formaldehyde resin acid, and hydrocarbons.
  • the proton exchange membrane 602 is used to conduct the protons generated in the MEA 618 , and separate the fuel gases and the oxidant gases.
  • the catalyst layer 608 includes catalyst materials and carriers.
  • the catalyst materials are selected from the group consisting of metal particles, such as platinum particles, gold particles or ruthenium particles.
  • the carrier is generally carbon particles, such as graphite, carbon black, carbon fiber or carbon nanotubes.
  • the gas diffusion layer 606 is the carbon nanotube film produced in the present embodiment.
  • the FFP 610 is made of metals or conductive carbon materials. Each FFP 610 is disposed on a surface of each electrode 604 facing away from the proton exchange membrane 602 .
  • the FFP 610 has at least one flow field groove 616 .
  • the flow field groove 616 is contacted with the gas diffusion layer 606 .
  • the flow field groove 616 is used to transport the fuel gases, the oxidant gases, and the reaction product (i.e. water).
  • the CCP 612 is made of conductive materials. Each CCP 612 is disposed on a surface of each FFP 610 facing away from the proton exchange membrane 602 . Thus, the CCP 612 is used to collect and conduct the electrons in the work process of MEA 618 .
  • the related support equipments 614 include blowers, valves, and pipelines. The blower is connected with the flow field plate 610 by the pipelines. The fuel gases and the oxidant gases are blown by the blowers
  • fuel gases i.e. hydrogen
  • oxidant gases i.e. pure oxygen or air containing oxygen
  • hydrogen is applied to an anode; and oxygen to a cathode.
  • a reaction of each hydrogen molecule is as follows: H 2 ⁇ 2H + +2e.
  • the hydrogen ions generated by the above-described reaction reach the cathode through the proton exchange membrane 602 .
  • the electrons generated by the reaction also arrive at the cathode by an external electrical circuit.
  • oxygen is also applied to the cathode.
  • the oxygen is reacted with the hydrogen ions and electrons as follows:
  • the electrons form an electrical current, thereby being able to output electrical energy. Accordingly, the water generated by the reaction penetrates the gas diffusion layer 606 and the flow field plate 610 , thereby removing out of the MEA 608 . From the above-described process, it is known that the gas diffusion layer 606 reacts as a channel for the fuel gases, oxidant gases, as well as the electrons. Fuel gas and oxidant gases from the gas diffusion layer 606 arrive at the catalyst layer; and the electrons through the gas diffusion layer 606 are connected with the external electrical circuit.
  • the gas diffusion layer 606 includes the carbon nanotube film.
  • the carbon nanotube film includes a plurality of carbon nanotubes tangled with each other. The adjacent carbon nanotubes are combined and tangled by van der Waals attractive force, thereby forming a network structure/microporous structure. Further, the carbon nanotubes in the carbon nanotube film are isotropic, uniformly dispersed, and arranged in disorder. Thus, the carbon nanotube film has the microporous structure and a large specific surface area. As such, in one side of MEA 618 , the hydrogen can be effectively and uniformly diffused in the carbon nanotube film. The hydrogen fully contacts with metal particles in the catalyst layer 608 . Thus, the catalytic reaction activity of the metal particles with the hydrogen is enhanced.
  • the oxidant gases are also uniformly diffused to the catalyst layer 608 through the carbon nanotube film, thereby fully contacting with the metal particles of the catalyst layer 608 .
  • the catalytic reaction activity of the metal particles with the hydrogen ions and electrons is enhanced. Due to the carbon nanotube film having good conductivity, the electrons needed or generated in the reactions are quickly conducted by the carbon nanotube film.
  • a method for making the carbon nanotube film to be used as the gas diffusion layer 606 has the following virtues. Firstly, through flocculating, the carbon nanotubes are bundled together by van der Walls attractive force to form a network structure/floccule structure. Thus, the carbon nanotube film is very durable. Secondly, the carbon nanotube film is very simply and efficiently produced by the method. A result of the production process of the method, is that thickness and surface density of the carbon nanotube film are controllable.

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US9419286B2 (en) * 2011-01-13 2016-08-16 GM Global Technology Operations LLC Wet lamination process for reducing mud cracking in fuel cell components
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