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WO2019030557A1 - Couches de catalyseurs d'anode de réaction d'évolution d'oxygène autonomes pour piles à combustible - Google Patents

Couches de catalyseurs d'anode de réaction d'évolution d'oxygène autonomes pour piles à combustible Download PDF

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Publication number
WO2019030557A1
WO2019030557A1 PCT/IB2018/000705 IB2018000705W WO2019030557A1 WO 2019030557 A1 WO2019030557 A1 WO 2019030557A1 IB 2018000705 W IB2018000705 W IB 2018000705W WO 2019030557 A1 WO2019030557 A1 WO 2019030557A1
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WO
WIPO (PCT)
Prior art keywords
oer
catalyst
catalyst layer
anode
anode catalyst
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Ceased
Application number
PCT/IB2018/000705
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English (en)
Inventor
Yuquan ZOU
Hao Zhang
Scott Mcdermid
Sumit Kundu
Dorina Manolescu
Yunsong Yang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mercedes Benz Group AG
Ford Motor Co
Original Assignee
Daimler AG
Ford Motor Co
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Filing date
Publication date
Application filed by Daimler AG, Ford Motor Co filed Critical Daimler AG
Publication of WO2019030557A1 publication Critical patent/WO2019030557A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • 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
    • H01M4/8828—Coating with slurry or ink
    • 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
    • H01M4/8846—Impregnation
    • 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
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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

  • This invention relates to bilayer anode catalyst layer designs for providing voltage reversal tolerance in solid polymer electrolyte membrane fuel cell stacks.
  • the invention relates to discrete anode catalyst layers comprising OER catalyst for such designs.
  • Fuel cells electrochemically convert a fuel reactant (e.g. hydrogen) and an oxidant reactant (e.g. oxygen or air) to generate electric power.
  • Solid polymer electrolyte fuel cells are a type of fuel cell which employs a proton conducting, solid polymer membrane electrolyte (e.g. perfluorinated sulfonic acid ionomer) between cathode and anode electrodes. Gas diffusion layers are typically employed adjacent each of the cathode and the anode electrodes to improve the distribution of gases to and from the electrodes.
  • flow field plates comprising numerous fluid distribution channels for the reactants are provided adjacent the gas diffusion layers to distribute fuel and oxidant to the respective electrodes and to remove by-products of the electrochemical reactions taking place within the fuel cell.
  • Water is the primary byproduct in a cell operating on hydrogen and air reactants. Because the output voltage of a single cell is of order of 1 V, a plurality of cells is usually stacked together in series for commercial applications. Fuel cell stacks can be further connected in arrays of interconnected stacks in series and/or parallel for use in automotive applications and the like.
  • CCMs catalyst boated membranes
  • an anode and a cathode are bonded in layer form to opposite sides of a membrane electrolyte layer.
  • Each of the anode and cathode comprise appropriate catalysts.
  • a CCM is a bonded, layered assembly comprising an anode catalyst layer, a membrane electrolyte layer, and a cathode catalyst layer.
  • the components in a CCM are all thin and relatively fragile. Further, the electrolyte membrane is typically not dimensionally stable and can swell when in contact with solvents used in typical inks or coatings. Thus it can be challenging to find suitable techniques for mass production of CCMs. Among the many known methods for preparing CCMs, decal transfer methods are probably the most commonly used. However, techniques have been developed which employ reinforcement layers to assist both in CCM production as well as to improve the CCM's mechanical properties.
  • WO2013/064640 discloses an "integral" approach to first coat the cathode layer onto a supporting substrate, followed by electrolyte membrane coating, in which an expanded polytetrafluoroethylene (ePTFE) substrate pre-impregnated with ionomer dispersion is introduced and then adhered to the cathode layer. Finally, the anode layer is coated onto the membrane ionomer layer to form the CCM.
  • ePTFE expanded polytetrafluoroethylene
  • ionomer dispersion is introduced and then adhered to the cathode layer.
  • the anode layer is coated onto the membrane ionomer layer to form the CCM.
  • ePTFE expanded polytetrafluoroethylene
  • US20130202986 discloses a fuel cell construction comprising a reinforced electrode assembly comprising first and second porous reinforcement layers.
  • the incorporation of one or more reinforcement layers in a CCM advantageously provides improved mechanical strength and in-plane hydration stability (i.e. the dimensional stability of the CCM in the planar directions as a function of hydration state). This is important with regards to long-term durability of commercial fuel cell stacks.
  • a reinforcement layer e.g. ePTFE
  • the swelling of the ionomer layer can be constrained by such a reinforcement layer.
  • a problem associated with large series stacks of fuel cells is that, if for some reason a cell (or cells) in the series stack is not capable of delivering the same current being delivered by the other cells in the stack, that cell or cells may undergo voltage reversal. Depending on the severity and duration of the voltage reversal, the cell may be irreversibly damaged and there may be an associated loss in cell and stack performance. Thus, it can be very important in practical applications for the cells in large series stacks to either be protected against voltage reversal or alternatively to have a high tolerance to voltage reversal.
  • a voltage reversal condition can arise for instance due to a fuel starvation condition existing on the fuel cell anode (i.e. where the anode receives insufficient fuel for intended operation).
  • a fuel starvation condition can happen during start up from below freezing temperatures as a result of ice blockages in the anode, or during operation at normal operating temperatures as a result of anode "flooding" (where liquid water blocks passageways in the anode). It is well recognized that such conditions can lead to cell voltage reversal due to the associated rise of anode potential, and further can lead to corrosion of the carbon supports which are typically used to support the anode catalyst (typically platinum). As a consequence of this corrosion, a loss in effective platinum surface area occurs at the anode and cell function is degraded. Therefore, a voltage reversal tolerant anode is an important design requirement for the anodes in commercial fuel * cell stacks.
  • the OER catalyst may be mixed directly with the primary anode catalyst (e.g. carbon supported Pt catalyst).
  • the secondary OER catalyst may be incorporated in a distinct, separate layer (e.g. a bilayer design as disclosed in US2013/002289).
  • the former method is straightforward and more cost-effective compared to the latter.
  • the observed activity of the OER catalyst using the latter method, and hence the reversal tolerance of fuel cells in which the OER catalyst appears in a separate layer is significantly improved compared to that using the former admixed method.
  • the structure of the anode layer as a whole can have a significant impact on the effectiveness and function of any incorporated OER catalyst.
  • hydrocarbon ionomer in anodes comprising OER catalyst is beneficial because the OER catalyst is stabilized by the presence of hydrocarbon type of ionomer.
  • the use of hydrocarbon ionomer can significantly slow down the dissolution and migration of the catalyst metal when compared to that observed using the more traditional polyfluorosulfonic acid ionomer (PFSA).
  • PFSA polyfluorosulfonic acid ionomer
  • Free-standing oxygen evolution reaction (OER) anode catalyst layers for a solid polymer electrolyte fuel cell and methods for making them have been developed.
  • the anode layers comprise a porous polymer sheet (e.g. expanded polytetrafluoroethylene) and a mixture comprising an OER catalyst and a hydrocarbon ionomer which is impregnated in the pores of the porous polymer sheet.
  • a porous polymer sheet e.g. expanded polytetrafluoroethylene
  • hydrocarbon ionomer which is impregnated in the pores of the porous polymer sheet.
  • a suitable porous polymer sheet can be greater than 85% porous and can have an average pore size of about 600 nm.
  • a suitable OER catalyst comprises iridium oxide. The average particle size of the OER catalyst can be about 200 nm and the loading of the OER catalyst can be from about 20 to 50 micrograms/cm 2 and particularly from about 30 to 35 micrograms/cm 2 .
  • a suitable hydrocarbon ionomer comprises a suitable sulfonated polyphenylene (e.g. as for instance disclosed in CA2933122). And in the mixture, additional ionomers may be included, such as perfluorosulfonic acid ionomer or another type of hydrocarbon ionomer.
  • a suitable weight ratio of the OER catalyst to the hydrocarbon ionomer is about 5: 1.
  • An OER anode catalyst layer of the invention may be employed in a catalyst coated membrane assembly (CCM) for a solid polymer electrolyte fuel cell.
  • CCM catalyst coated membrane assembly
  • Such a CCM comprises a solid polymer electrolyte membrane comprising a proton-conducting membrane ionomer, and a cathode and a bilayer anode bonded to opposite sides of the solid polymer electrolyte membrane.
  • the cathode comprises a cathode oxygen reduction reaction (ORR) catalyst.
  • the bilayer anode comprises a hydrogen oxidation reaction (HOR) anode catalyst layer adjacent the electrolyte membrane and an OER anode catalyst layer of the invention located away from the electrolyte membrane.
  • HOR hydrogen oxidation reaction
  • the HOR catalyst used can comprise platinum supported on carbon particles.
  • OER anode catalyst layer of the invention can be made using simple methods suitable for mass production purposes.
  • an OER anode catalyst layer can be made via the following steps:
  • an OER anode catalyst layer can be made via the following steps: preparing an ink comprising the OER catalyst, the hydrocarbon ionomer, and a solvent, coating the ink onto the porous polymer sheet whereby the dispersion impregnates the pores of the porous polymer sheet, and
  • Figure 1 shows a schematic illustration of a solid polymer fuel cell comprising a bilayer anode which includes an OER anode catalyst layer of the invention.
  • Figure 2a shows a schematic illustration of a first method for preparing a free-standing OER anode catalyst layer of the invention.
  • Figure 2b shows a schematic illustration of a second method for preparing a free-standing OER anode catalyst layer of the invention.
  • Figure 3 compares the polarization curves (voltage versus current density) of a comparative fuel cell to a fuel cell of the invention.
  • HOR refers to "hydrogen oxidation reaction” and a HOR catalyst is specifically selected for oxidizing fuel at the anode in a solid polymer electrolyte fuel cell.
  • a suitable HOR catalyst is platinum, or more preferably carbon supported platinum. However, various other precious or non-precious metals, alloys, or mixtures may be considered.
  • OER refers to "oxygen evolution reaction” and an OER catalyst is specifically selected to hydrolyze water at the anode in a solid polymer electrolyte fuel cell.
  • an OER catalyst is defined herein to be a catalyst other than the HOR catalyst (i.e. is materially different from the HOR catalyst used in the anode) and is selected to be more effective at water hydrolysis than the HOR catalyst.
  • a suitable OER catalyst is iridium oxide. However, various other oxides, compositions, alloys, or mixtures may be considered.
  • ORR refers to "oxygen reduction reaction" and an ORR catalyst is specifically selected for reducing oxidant at the cathode in a solid polymer electrolyte fuel cell.
  • a suitable ORR catalyst is platinum, or more preferably carbon supported platinum. However, various other precious or non-precious metals, alloys, or mixtures may be considered.
  • FIG. 1 A schematic illustration of an exemplary solid polymer fuel cell of the invention is shown in Figure 1.
  • a single such fuel cell is shown and it comprises a CCM of the invention, which in turn comprises a bilayer anode that includes an OER anode layer of the invention.
  • fuel cell 1 comprises CCM 2 which is located between a pair of gas diffusion layers (GDLs), namely anode GDL 10 and cathode GDL 11. In turn, this assembly is located between a pair of flow field plates, namely fuel flow field plate 12 and oxidant flow field plate 13.
  • GDLs gas diffusion layers
  • this assembly is located between a pair of flow field plates, namely fuel flow field plate 12 and oxidant flow field plate 13.
  • CCM 2 comprises solid polymer electrolyte membrane 8, cathode catalyst layer 9, and bilayer anode 3. Cathode catalyst layer 9 and bilayer anode 3 are bonded to opposite sides of solid polymer electrolyte membrane 8.
  • Bilayer anode 3 comprises HOR anode catalyst layer 4 adjacent electrolyte membrane 8 and OER anode catalyst layer 5 located away from electrolyte membrane 8 (and adjacent anode GDL 10 in the exemplary embodiment of Figure 1).
  • OER anode catalyst layer 5 comprises porous polymer sheet 6 (e.g. expanded PTFE) which has been impregnated with mixture 7 comprising particulate OER catalyst (e.g. Ir02) and hydrocarbon ionomer (e.g. a suitable sulfonated Diels-Alder polyphenylene as described in CA2933122 which describes the making of specific polyphenylenes via a Diels-Alder reaction).
  • the fuel and oxidant flow field plates (12, 13) would typically be mated together to form a unitary bipolar plate.
  • the bipolar plate would also typically incorporate coolant flow fields between the mated plates to allow for coolant flow therein and thus for efficient heat removal from the stack during operation.
  • the porous polymer sheet in OER anode catalyst layer 5 provides mechanical support for mixture 7 and allows for it to be made separate from CCM 2 and even as a separate component for bilayer anode 3.
  • a suitable reinforcing porous polymer sheet material for use in the present invention is expanded PTFE (ePTFE).
  • porous expanded polymer sheet such as porous polypropylene (PP), porous polyvinylidene fluoride (PVDF), porous polyethersulfone (PES), and the like can be readily employed instead.
  • other types of porous polymer sheet may be considered (i.e. porous polymer sheet other than expanded polymer sheet).
  • porous electrospun sheet and porous sheet made from nano- fibres may be considered.
  • representative sheet porosities range from about 60 to 90%, thicknesses from about 4 to 8 micrometers thick, and average pore sizes from about 0.2 to 1 micrometers although other porosities, thicknesses, and average pore sizes may be considered.
  • suitable OER anode catalyst layers can be made using ePTFE that is 89% porous, 5 micrometers thick and has an average pore size of 600 nm.
  • the OER catalyst used in OER anode catalyst layer 5 can be any suitable secondary catalyst material for promoting water hydrolysis at the anode (e.g. as described in the aforementioned US6517962 and US6936370) and thereby providing improved tolerance to voltage reversal. Iridium and its oxides or mixed oxides comprising iridium can be particularly desirable.
  • the hydrocarbon ionomer used in OER anode catalyst layer 5 can be any suitable such ionomer, e.g. sulfonated Diels-Alder polyphenylene, or combination of such ionomers.
  • other ionomer types e.g. PFSA ionomer
  • the ionomers employed in the OER anode catalyst layer serve as a binder as well as for providing ionic access to the OER catalyst. Preferably then a sufficient amount is employed for these purposes. However it is also important to allow for adequate flow of gases through the OER anode catalyst layer. As illustrated in the following Examples, it is possible to achieve all these requirements using an appropriate weight ratio of OER catalyst to hydrocarbon ionomer in mixture 7 (e.g. about 5: 1).
  • the use of a porous polymer sheet in the OER anode catalyst layer serves to reinforce it and also to reinforce the bilayer anode and CCM in which it is incorporated.
  • Several characteristics are improved as a result (e.g. handling characteristics, hydration stability).
  • the use of a separate layer for a given amount of OER catalyst in the anode can provide for superior reversal tolerance compared to using an admixture of HOR and OER catalysts in the anode.
  • the use of hydrocarbon ionomer in the OER anode catalyst layer can significantly slow down the dissolution and migration of the catalyst metal when compared to that observed using the more traditional PFSA ionomer.
  • OER anode catalyst layer 5 may be fabricated in at least two simple ways that are suitable for purposes of mass production.
  • Figure 2 shows schematic illustrations of two methods for preparing a free-standing OER anode catalyst layer of the invention. The method of Figure 2a involves uptake of a dispersion into porous polymer sheet 6 while the method of Figure 2b involves coating a dispersion onto porous polymer sheet 6.
  • OER catalyst dispersion 15 is prepared in step 21 which comprises a dispersion of OER catalyst 7 in a solution comprising hydrocarbon ionomer dissolved in a suitable carrier solvent (e.g. an alcohol and water).
  • a suitable carrier solvent e.g. an alcohol and water.
  • the hydrocarbon ionomer also usefully stabilizes the dispersion for manufacturing purposes. As illustrated in the Examples below, care must be taken not to use an excessive amount of ionomer since too much ionomer in the product catalyst layer can adversely affect gas permeability therethrough.
  • a continuous web of porous polymer sheet 6 is immersed in a bath of OER catalyst dispersion 15 in immersing step 22a whereby the pores of porous polymer sheet 6 are fully impregnated with dispersion 15.
  • the web is then continuously dried at step 23 to remove the carrier solvent to produce a continuous web of OER anode catalyst layer which can be subsequently cut as desired into free-standing OER anode catalyst layers 5.
  • dispersion 15 now serves as a catalyst coating ink.
  • a continuous web of porous polymer sheet 6 is directed against backer roll 30 while coating head 31 applies a continuous coating of dispersion 15 thereto in coating step 22b.
  • the web is then continuously dried at step 23 to remove the dispersion solvent to produce a continuous web of OER anode catalyst layer which can be subsequently cut as desired into free-standing OER anode catalyst layers 5.
  • OE anode catalyst layer samples were prepared according to the method generally shown in Figure 2b.
  • the porous polymer sheet employed was an expanded PTFE sheet with thickness of about 5 micrometers, porosity of 89%, and an average pore size of 600 nm.
  • Two similar dispersions were prepared which comprised iridium oxide (IrC ) particulate catalyst as the OER catalyst, carrier solvent mixtures of isopropyl alcohol and water (in a 3: 1 weight ratio respectively), but differing amounts of sulfonated Diels-Alder polyphenylene hydrocarbon ionomer.
  • the IrC>2 catalyst had an average particle size of about 200 nm.
  • the weight concentration of catalyst in the dispersions was about 5%.
  • the weight concentrations of the hydrocarbon ionomer in the dispersions was either about 1% or 0.5%. (Thus, the weight ratio of OER catalyst to hydrocarbon ionomer in the former dispersion would be about 5: 1.)
  • the ion exchange capacity (IEC) of the sulfonated Diels-Alder polyphenylene hydrocarbon ionomer was between about 2.2 and 2.4 meq/g.
  • a Mayer bar coating method was used to apply the dispersions to expanded PTFE samples mounted on backing substrates.
  • the dispersions readily penetrated the pores of the e-PTFE and thereafter the solvent was removed by drying.
  • the loading of applied OER catalyst in the dried samples was determined to be about 32 micrograms/cm 2 .
  • the produced anode catalyst layer samples were easily peeled off the backing substrate, were self-supporting, and could be handled manually without any damage or failure.
  • Through-plane gas permeability values were measured for representative samples from each type of dispersion and were compared to values obtained from two different but conventional anode gas diffusion layers and the supplied e-PTFE prior to coating. The measurements were made using a standard Gurley permeability test procedure (in which a fixed volume of air is pushed through the samples under standard conditions and the time taken to do so is indicative of relative gas permeability).
  • the as-supplied e-PTFE had a Gurley time of about 2 seconds.
  • the two conventional anode GDLs had Gurley times of about 85 and 94 seconds.
  • the representative samples prepared in accordance with the invention had Gurley times of about 64 and 102 seconds for the dispersions made with 0.5% and 1.0% hydrocarbon ionomer concentrations respectively.
  • Experimental fuel cells were then prepared to roughly compare the performance and voltage reversal tolerance characteristics of cells made with OER anode catalyst layers of the invention to the characteristics of conventional fuel cells comprising OER anode catalyst as an admixture in the anode.
  • the former cells comprised anode catalyst layers as prepared above using a 1% hydrocarbon ionomer concentration and are denoted as Inventive fuel cells in the following.
  • the latter cells are denoted as Comparative fuel cells in the following.
  • the anodes in both types of fuel cells employed equal amounts of Pt catalyst and ⁇ 3 ⁇ 4 catalyst as HOR and OER catalysts respectively. Further, each type of fuel cell used the same catalyst loadings.
  • the Inventive fuel cells comprised a bilayer anode structure as shown in Figure 1.
  • the Comparative fuel cells instead comprised a single anode layer comprising a simple admixture of the HOR and OER catalyst. Otherwise, the construction of the two types of cells was similar and conventional.
  • Figure 3 compares the polarization curves (voltage versus current density) of a Comparative fuel cell to an Inventive fuel cell under conventional operating conditions for automotive applications (e.g. using hydrogen and air as the supplied reactants at 50% RH, and at a temperature of 70°C).
  • the performance of the Inventive fuel cell was slightly inferior to that of the Conventional fuel cell but is roughly the same.
  • similar results were obtained. Namely, the performance of the Inventive fuel cell was somewhat inferior to that of the Conventional fuel cell but still similar enough.
  • the voltage reversal characteristics of cells were determined using testing that simulates an extended reversal event occurring in a cell in a stack that is undergoing fuel starvation.
  • the cells are first operated normally at a current density of 1 A/cm 2 . Then the current is turned off, the reactant supply to the anode is switched from hydrogen to nitrogen instead, and 0.2 A/cm 2 is forced through the cells, thereby subjecting it to voltage reversal conditions.
  • the cell voltage would roughly plateau at a value between 0 and about -3 volts for a variable amount of time and then drop off suddenly to a value much less than -5 V, at which point testing ended.
  • the length of time to this sudden drop off point is representative of the cell's ability to tolerate voltage reversal.
  • an Inventive fuel cell exhibited a reversal time of 360 minutes while the Comparative fuel cell exhibited a reversal time of 850 minutes. While the reversal tolerance of the Inventive fuel cell was thus somewhat inferior compared to that of the Conventional fuel cell, it should be. noted that a similar fuel cell without any added OER anode catalyst only exhibits a reversal time of a mere 10 minutes.

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Abstract

L'invention concerne des couches de catalyseur d'anode de réaction d'évolution d'oxygène (OER) autonomes pour une pile à combustible à électrolyte polymère solide et des procédés de fabrication de celles-ci. Les couches de catalyseur d'anode comprennent une feuille de polymère poreux (par exemple du PTFE expansé) et un mélange comprenant un catalyseur OER et un ionomère hydrocarboné qui est imprégné dans les pores de la feuille de polymère poreux. L'utilisation d'une telle couche de catalyseur d'anode OER séparée dans un ensemble membrane revêtu de catalyseur d'une pile à combustible offre une meilleure tolérance d'inversion de tension que les mélanges et l'utilisation de l'ionomère hydrocarboné peut ralentir la dissolution du catalyseur OER. En outre, les procédés de préparation sont appropriés pour une production de masse.
PCT/IB2018/000705 2017-08-11 2018-06-15 Couches de catalyseurs d'anode de réaction d'évolution d'oxygène autonomes pour piles à combustible Ceased WO2019030557A1 (fr)

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CN110534761A (zh) * 2019-09-25 2019-12-03 上海电气集团股份有限公司 一种燃料电池催化剂浆料、电极及其制备方法
CN113130954A (zh) * 2019-12-31 2021-07-16 现代自动车株式会社 能够防止催化剂中毒的用于燃料电池的电解质膜及其制备方法
US11967721B1 (en) * 2022-11-23 2024-04-23 GM Global Technology Operations LLC Battery with positive electrodes

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