WO2020251492A2 - Application de polymère de polydiméthylsiloxane (pdms) hydrophobe à diverses quantités dans une couche catalytique d'une pile à combustible de type pem - Google Patents

Application de polymère de polydiméthylsiloxane (pdms) hydrophobe à diverses quantités dans une couche catalytique d'une pile à combustible de type pem Download PDF

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Publication number
WO2020251492A2
WO2020251492A2 PCT/TR2020/050479 TR2020050479W WO2020251492A2 WO 2020251492 A2 WO2020251492 A2 WO 2020251492A2 TR 2020050479 W TR2020050479 W TR 2020050479W WO 2020251492 A2 WO2020251492 A2 WO 2020251492A2
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solution
polymer
catalyst layer
catalyst
pdms
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PCT/TR2020/050479
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WO2020251492A3 (fr
Inventor
Ayşe BAYRAKÇEKEN YURTCAN
Hande UNGAN
Ayşenur ÖZTÜRK
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Atatürk Üni̇versi̇tesi̇ Bi̇li̇msel Araştirma Projeleri̇ Bi̇ri̇mi̇
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Publication of WO2020251492A2 publication Critical patent/WO2020251492A2/fr
Publication of WO2020251492A3 publication Critical patent/WO2020251492A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8867—Vapour deposition
    • H01M4/8871—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8896—Pressing, rolling, calendering
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
    • 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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • 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

Definitions

  • Invention relates to a catalyst solution convenient for use in fuel cells.
  • Invention particularly relates to preparation of a catalyst layer solution comprising hydrophobic polydimethylsiloxane (PDMS) polymer at various amounts convenient for use in PEM fuel cells.
  • PDMS polydimethylsiloxane
  • Fuel cells is the most popular application of hydrogen energy.
  • Today fuel cells has found more application fields as power generation technology which are efficient, economical, silence and compatible with environment.
  • Fuel cells are power sources converting chemical energy of fuel into usable energy in the forms of electric and heat without need for combustion and without use of any intermediate components.
  • Particularly PEM (Proton Exchange Membrane) fuel cells are considerably convenient for portable and mobileapplications due to low working temperatures.
  • the first and most common one is treatment of PEM fuel cell components with hydrophobic materials
  • the second one is changing operating conditions of PEM fuel cell.
  • various fuel cell components gas diffusion layer, microporous layer, catalyst layer, polymer electrolyte membrane and bipolar layers etc.
  • PTFE polytetrafluoroethylene
  • the hydrophobic material in number two after PTFE polymer is fluorinated ethylene propylene (FEP) polymer which is also a kind of fluoropolymers.
  • FEP fluorinated ethylene propylene
  • patent document numbered US5272017A is about the preparation of membrane and electrode assemblies for use in electrochemical cells having solid polymer electrolyte membranes.
  • the each electrodes comprise a respective group of finely divided carbon particles, very finely divided catalytic particles supported on internal and external surfaces of these carbon particles and a proton conductive material interwined with these catalytic and carbon particles.
  • the mentioned polymer is polytetrafluoroethylene (PTFE) polymer.
  • Graphic A of Figure 2 shows cell performance of PBI polymer and Graphic B shows cell performance of PTFE polymer in catalyst layer at different percentages by weight.
  • triangle represents 5.1 % by weight
  • circle represents 10.1% by weight
  • down facing triangle represents 12% by weight
  • lastly cross represents 15.1% by weight.
  • the present invention relates to catalyst layer solution which meets the needs mentioned above, eliminates all disadvantages and provides some additional advantages.
  • Primary purpose of the invention is to develop a catalyst layer solution providing increase in performance of PEM fuel cell which is a clean and sustainable energy source by means of its polymer content.
  • Another purpose of the invention is to develop a catalyst layer solution meeting energy need at a high efficiency by means of its low polymer content.
  • a further purpose of the invention is to develop a catalyst layer solution maximising cell performance and keeping membrane humidified by establishing a good and effective water balance by means of its polymer content.
  • a further purpose of the invention is to develop a catalyst layer solution eliminating blocking gas flow pathways because of excess water amount and providing occurrence of half cell reaction in electrode without interruption by means of its polymer content.
  • present invention develops a catalyst layer solution appropriate for use in PEM fuel cells and this solution comprises National solution as binder and polydimethylsiloxane (PDMS) polymer as hydrophobic material.
  • the invention also relates to a method for the preparation of a membrane electrode assembly (MEA), which is formed by pressing anode and cathode electrodes having a catalyst layer on their surfaces onto both sides of polymer electrolyte membrane, in where electrochemical half cell reactions occur, which is appropriate for the use in PEM fuel cells.
  • MEA membrane electrode assembly
  • Figure 1 a is graphic showing performance of cell described under document D1 wherein PTFE polymer is used
  • Figure 1 b is graph showing performance of cell described under the invention wherein PDMS polymer is used
  • Figure 2 is a graph showing effect of use of two different hydrophobic materials in catalyst layer at varying percentages on cell performance in document D2
  • FIG. 3 is a image of membrane electrode assembly (MEA) of PEM fuel cell
  • Figure 4 is a image of measurements of contact angle on catalyst layer surfaces
  • Figure 5 is a flow chart showing part of invention in fuel cell
  • FIG 6a is an illustrative drawing of membrane electrode assembly (MEA)
  • Figure 6b is an illustrative drawing of single fuel cell
  • Figure 6c is an illustrative drawing of fuel cell test station
  • a catalyst layer solution (S) convenient for use in PEM fuel cells which is being subject of this invention have been disclosed solely for the purpose of better understanding of the subject and described in a manner not causing any restrictive effect.
  • Present invention develops a catalyst layer solution (S) convenient for use in PEM fuel cells and this solution (S) comprises National solution (2) as binder and polydimethylsiloxane (PDMS) polymer (3) as hydrophobic material.
  • PDMS polydimethylsiloxane
  • PDMS polymer (3) is a silicone type polymer with hydrophobic nature in which methyl (-CH3) groups are circulating around Si-O-Si main chain freely. It is different from other organic materials with its physical and chemical properties such as high and low temperature stability, good dielectric features, low interface energy, high surface activity, inertness, transparency. PDMS polymer (3) has also considerably hydrophobic property and thanks to this feature, it also provides hydrophobic property for the structure in where it is used even in low amounts.
  • PDMS polymer (3) provides super hydrophobic/hydrophobic features to surfaces which it is applied on and this can also be possible when PDMS polymer (3) is used in low amounts.
  • developed catalyst layer solution (S) comprises PDMS polymer (3) in weight percentages of 5%, 10% and 20% according to total solution (S) weight.
  • Contact angle measurements were made on the catalyst layer (D) surfaces prepared in this way and results were shown in Figure 4. As it can be seen from the figure, following water dripping, spherical shape is formed on all surfaces. This case shows that catalyst layer (D) surface gets more hydrophobic when PDMS percentage increases.
  • the developed catalyst layer solution (S) comprises carbon supported platinum catalyst (1 ).
  • the catalyst (1 ) functioning as catalyst for electrochemical reactions occurring at PEM fuel cells is preferably Tanaka (67% Pt) catalyst commercially purchased, and loading amount of this catalyst (1 ) to anode (A) and cathode (B) electrode at PEM fuel cell is preferably 0,4 mg Pt/cm 2 .
  • the developed catalyst layer solution (S) also comprises National solution (2) as binder and this binder (2) makes contribution to electrical conductivity inside catalyst layer (D) and facilitates the adsorption of platinum nano particles to electrode surface.
  • the developed catalyst layer solution (S) also comprises at least a solvent.
  • the solvents are preferably 2-propanol (4) and distilled water (5).
  • the ratio between 2-propanol (4) and distilled water (5) that can be selected as solvents, is preferably 2:1 by volume.
  • present invention develops a membrane electrode assembly (MEA) (9), which is formed by compression of anode (A) and cathode (B) electrodes having catalyst layer (D) on their surfaces onto both sides of polymer electrolyte membrane (C), in where electrochemical half cell reactions occur, which is convenient for use in PEM fuel cells; the mentioned catalyst layer (D) was prepared by a catalyst layer solution (S) comprising National solution (2) as binder and polydimethylsiloxane (PDMS) polymer (3) as hydrophobic material.
  • MEA membrane electrode assembly
  • MEA(9) has an embodiment which is formed by compression of anode (A) and cathode (B) electrodes on both sides of polymer electrolyte membrane, having gas channels (G) upon, comprising a gas inlet (E) providing gas entrance into these channels (G) and a gas outlet (F) providing exit of gas from these channels (G).
  • catalyst layer (D) on the surface of electrodes in MEA structure.
  • the membrane electrode assembly (MEA) (9) was illustratively shown in Figure 3. Water management should be well done in order to execute electrochemical half cell reactions properly and achieve high cell performance.
  • hydrophobic material is included in catalyst layer and mostly PTFE polymer is preferred for this.
  • MEA membrane electrode assembly
  • an application of the invention is executed as follows: First of all, materials to form solution (S) for PEM fuel cell catalyst layer are provided.
  • carbon supported catalyst (1 ) containing platinum at 67% by mass and preferably, commercial Nafion solution (2) containing Nafion at 15% by mass are weighed in needed quantities and put into bottle.
  • Preferred loading amount of carbon supported platinum catalyst (1 ) in each electrode, namely anode (A) and cathode (B), is 0.4 mg Pt/cm 2 .
  • the active area in fuel cell is 4.41 cm 2
  • the required amount of carbon supported platinum catalyst (1 ) is calculated on the basis of two values.
  • catalyst layer solution (S) is formed by preferably 2-propanol (4) and distilled water (5) into bottle as solvents preferably 2:1 ratio by volume to form final catalyst layer solution (S).
  • Prepared catalyst layer solution (S) is mixed for preferably 3-4 minutes by the help of a mixer (preferably homogenizer) and homogenous solution is obtained.
  • an air compressor spray gun is used to transfer it onto a gas diffusion layer (6) (GDL 34 BC) purchased commercially.
  • GDL 34 BC gas diffusion layer (6)
  • prepared homogenous solution is put into reservoir of gun and is sprayed onto gas diffusion layer (6) to form catalyst layer (D).
  • Gas diffusion layer (6) is weighed when it is empty before spraying and also is weighed during spraying at certain time intervals and it is checked for if desired weight for catalyst layer (D) is achieved or not. When the desired weight is reached, spraying process is stopped.
  • weight of catalyst layer (D) weight of carbon supported platinum catalyst (1 ), dry National (2) and PDMS polymer (3) are taken into account. Since the spraying operation is conducted at preferably 60 ⁇ on a heater vacuum plate, 2-propanol (4) and distilled water (5) used as solvents are assumed to evaporated.
  • Catalyst layer (D) is prepared separately on gas diffusion layer (6) for anode (A) and cathode (B) electrodes.
  • Cathode electrode (B) catalyst layer (D) preparation procedure is as described at previous paragraph.
  • Procedure for the preparation of catalyst layer (D) for anode electrode (A) is the same except PDMS polymer (3).
  • Preference of PDMS polymer (3) at cathode electrode (B) is due to the fact that water is released as a result of oxygen reduction reaction occurring at this electrode and elimination of damage caused by such excess water by hydrophobic PDMS polymer (3).
  • Nafion membrane (C) is a perfluorosulfonic acid based polymeric membrane used as electrolyte in fuel cell. While it is allowing passing of only H + ions from anode (A) to cathode side, it does not allow passing of electrons. Electrons are transferred to cathode side by external circuit. Transfer of H + ions continue if the adequate humidification of Nafion membrane is provided during the supply of hydrogen gas.
  • Anode (A) and cathode (B) and Nafion membrane (C) are kept at hot-pressing device preferably at 130 ⁇ and at preferably 400 psi press ure preferably for 3-4 minutes.
  • a triple structure comprising anode-electrode(A) - Nafion membrane (C) - cathode electrode (B) is obtained as membrane electrode assembly (MEA) (9).
  • MEA membrane electrode assembly
  • Prepared MEA structures are now used in fuel cell. Performance measurements of the fuel cells are performed at Henatech trademark computer controlled fuel cell test station (7) which has maximum 600 W power. Hydrogen is supplied to anode side and oxygen gas is supplied to cathode side at 1 :1 stoichiometric ratio as reactant gases.
  • Catalyst layer solution developed under the invention provides establishment of a better and more effective water balance and thus generating power demand at higher efficiency from PEM fuel cell which are clean and sustainable power sources.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)
  • Catalysts (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention porte sur le développement d'une solution (S) de couche catalytique appropriée pour une utilisation dans des piles à combustible de type PEM, ladite solution (S) comprend une solution (2) de Nafion en tant que liant et un polymère (3) de polydimétilsiloxane (PDMS) en tant que matériau hydrophobe. L'invention porte également sur un ensemble membrane-électrode (MEA) (9), qui est formée par pressage d'électrodes, anode (A) et cathode (B) ayant une couche (D) de catalyseur sur leurs surfaces sur les deux côtés de la membrane (C) électrolytique polymère, des réactions électrochimiques de demi-cellules se produisant, ce qui est approprié pour une utilisation dans des piles à combustible de type PEM et un son procédé de préparation.
PCT/TR2020/050479 2019-06-13 2020-06-02 Application de polymère de polydiméthylsiloxane (pdms) hydrophobe à diverses quantités dans une couche catalytique d'une pile à combustible de type pem WO2020251492A2 (fr)

Applications Claiming Priority (2)

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TR2019/08785 2019-06-13
TR201908785 2019-06-13

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WO2020251492A2 true WO2020251492A2 (fr) 2020-12-17
WO2020251492A3 WO2020251492A3 (fr) 2021-06-24

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3273591B2 (ja) * 1996-02-05 2002-04-08 本田技研工業株式会社 燃料電池用電極構造体の製造方法
TWI233233B (en) * 2003-12-31 2005-05-21 You-Jen Jang Manufacturing method of fuel cell part with capability of improving water drainage of electrode
JP4977911B2 (ja) * 2006-08-28 2012-07-18 アタカ大機株式会社 水素−空気／固体高分子電解質型可逆セルの空気極用の電極触媒粉末、それを用いた空気極を有する電極−電解質膜接合体（ｍｅａ）および可逆セル

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