|Numéro de publication||US8101319 B2|
|Type de publication||Octroi|
|Numéro de demande||US 10/850,550|
|Date de publication||24 janv. 2012|
|Date de dépôt||20 mai 2004|
|Date de priorité||20 mai 2004|
|État de paiement des frais||Payé|
|Autre référence de publication||CN1989643A, CN100565989C, DE112005001131T5, US20050260484, WO2005117173A2, WO2005117173A3|
|Numéro de publication||10850550, 850550, US 8101319 B2, US 8101319B2, US-B2-8101319, US8101319 B2, US8101319B2|
|Inventeurs||Youssef M Mikhail, Gayatri Vyas|
|Cessionnaire d'origine||GM Global Technology Operations LLC|
|Exporter la citation||BiBTeX, EndNote, RefMan|
|Citations de brevets (51), Citations hors brevets (14), Référencé par (5), Classifications (20), Événements juridiques (13)|
|Liens externes: USPTO, Cession USPTO, Espacenet|
The present invention relates to electrochemical cells, and more particularly to electrically conductive fluid distribution elements and the manufacture and operation of fuel cells incorporating such fluid distribution elements.
Fuel cells have been proposed as a power source for electric vehicles and other applications. One known fuel cell is the PEM (i.e., Proton Exchange Membrane) fuel cell that includes a so-called MEA (“membrane-electrode-assembly”) comprising a thin, solid polymer membrane-electrolyte having an anode on one face and a cathode on the opposite face. The anode and cathode typically comprise finely divided carbon particles, very finely divided catalytic particles supported on the internal and external surfaces of the carbon particles, and proton conductive material intermingled with the catalytic and carbon particles. The MEA is sandwiched between gas diffusion media layers and a pair of electrically conductive contact elements which serve as current collectors for the anode and cathode, which may contain appropriate channels and openings therein for distributing the fuel cell's gaseous reactants (i.e. H2 and O2/air) over the surfaces of the respective anode and cathode.
Bipolar PEM fuel cell stacks comprise a plurality of the MEAs stacked together in electrical series while being separated one from the next by such current collector contact elements, which are further impermeable separator elements, known as bipolar plates. The bipolar plate has two working surfaces, one confronting the anode of one cell and the other confronting the cathode on the next adjacent cell in the stack, and electrically conducts current between the adjacent cells. Contact elements at the ends of the stack contact only the end cells and are referred to as end plates.
Electrical contact elements are often constructed from electrically conductive metal materials. In an H2 and O2/air PEM fuel cell environment, the bipolar plates and other contact elements (e.g., end plates) are in constant contact with highly acidic solutions (pH 3-5) and operate in a highly oxidizing environment, being polarized to a maximum of about +1 V (vs. the normal hydrogen electrode). On the cathode side the contact elements are exposed to pressurized air, and on the anode side exposed to super atmospheric hydrogen. Unfortunately, many metals are susceptible to corrosion in the hostile PEM fuel cell environment, and contact elements made therefrom either dissolve (e.g., in the case of aluminum), or form highly electrically resistive, passivating oxide films on their surface (e.g., in the case of titanium or stainless steel) that increases the internal resistance of the fuel cell and reduces its performance. Further, maintaining electrical conductivity through the gas diffusion media to the contact elements is of great importance in maintaining the flow of electrical current from each fuel cell. Thus, there is a need to provide electrically conductive elements that maintain electrical conductivity, resist the fuel cell hostile environment, and improve overall operational efficiency of a fuel cell.
One aspect of the present invention relates to a fluid distribution element for a fuel cell having a membrane electrode assembly (MEA), the element comprising a layer of electrically conductive porous media comprising carbon and one or more metallized regions on a surface of the layer confronting the MEA. The one or more metallized regions comprise an electrically conductive metal. Further, the one or more metallized regions contact a major surface of the MEA and form respective electrically conductive paths between the MEA and the porous media.
Another aspect of the present invention is a fuel cell assembly comprising a membrane electrode assembly (MEA) comprising an electrically conductive electrode. A layer of electrically conductive non-metallic porous media has a surface that faces the electrode. The surface also has one or more metallized regions comprising an electrically conductive metal. The conductive electrode is arranged in contact with the metallized regions to provide electrical contact between the layer and the conductive electrode. Thus, an electrical contact resistance between the electrode and the metallized regions of the layer is less as when compared to a comparative non-metallized layer of porous media.
Yet another aspect of the present invention relates to a method of operating a fuel cell comprising positioning an electrically conductive porous media layer between a membrane electrode assembly (MEA) and an electrically conductive substrate. The porous media layer has a first surface having ultra-thin metallized regions facing the MEA and a second surface that faces the conductive substrate. The metallized regions of the first surface are contacted with the MEA and the second surface is contacted with the substrate to form an electrically conductive path from the substrate through the porous media to the MEA. Electrons are conducted to or from the MEA via the path while operating the fuel cell.
In yet another aspect of the present invention, a method is provided for manufacturing an assembly for a fuel cell, comprising depositing an electrically conductive metal on a surface of an electrically conductive porous media to form one or more metallized regions having an ultra-thin thickness. The surface having the metallized regions is positioned adjacent to an electrode of a membrane electrode assembly (MEA). The electrode is contacted with the surface having the metallized regions to form an electrically conductive path between the substrate and the porous media.
In another aspect, the present invention provides a fuel cell assembly comprising a membrane electrode assembly (MEA) which comprises a first electrically conductive electrode and a second and opposite electrically conductive electrode. A first layer of electrically conductive non-metallic porous media has a surface facing and arranged in contact with the first electrode. The surface of the first layer has one or more metallized regions comprising an electrically conductive metal. A second layer of electrically conductive non-metallic porous media has a surface facing and arranged in contact with the second electrode, where the surface has one or more metallized regions comprising an electrically conductive metal. An electrical contact resistance between the first layer of porous media through the MEA to the second layer of porous media is less as when compared to a comparative assembly comprising a non-metallized first layer of porous media and a non-metallized second layer of porous media surrounding a similar MEA.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
The following description of the preferred embodiments is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
The present invention relates to an electroconductive fuel cell element, and more particularly to an improved fluid distribution media element for use in a fuel cell. For a better understanding of the present invention, a brief background is provided herein.
As best shown in
An interior metal spacer sheet 62 is positioned interjacent the exterior sheets 58 and 60 and includes a plurality of apertures 88 therein to permit coolant to flow between the channels 82 in sheet 60 and the channels 78 in the sheet 58 thereby breaking laminar boundary layers and affording turbulence which enhances heat exchange with the inside faces 90 and 92 of the exterior sheets 58 and 60, respectively. Thus, channels 78 and 82 form respective coolant flow fields at the interior volume defined by sheets 58 and 60. Alternate embodiments (not shown) comprise two stamped plates joined together by a joining process to form interior coolant flow fields.
In the present embodiment shown, there are two fluid distribution media layers 107 at each side of the MEA 100. A first fluid distribution media layer 120 confronts the anode 104, and a second fluid distribution media layer 122 confronts the cathode 106. The first fluid distribution media layer 120 comprises a first surface 124 and a second surface 126 opposite to the first surface 124. The second fluid distribution media layer 122 likewise comprises a third surface 128 and an opposite fourth surface 130. The first fluid distribution layer 120 is adjacent to the MEA 100, where the first surface 124 of the first media layer 120 confronts and preferably contacts the anode electrode 104. The second distribution layer 122 is also adjacent to the MEA 100 along the opposite cathode 106 side, where the third surface 128 of the second media layer 122 confronts and preferably contacts the cathode 106. The fluid distribution layers 107 preferably contact the respective electrodes 103 to form one or more electrical contact regions 129.
Each porous media layer 120,122 is bounded or sandwiched between the MEA 100 and a current collector separator plate substrate (132 or 134 analogous in function to 8 and 16 of
In electrochemical fuel cells 99 according to the present invention, the overall electrochemical reaction includes the oxidation of hydrogen to form water. The respective reactions at the anode (Reaction 1) and cathode (Reaction 2) are as follows:
H2→2H++2e − (Reaction 1)
½O2+2H++2e −→H2O (Reaction 2)
where the reactant fuel is hydrogen and the oxidant comprises oxygen (such as, air, for example). The protons released by the reaction at the anode 104 migrate through the MEA 100 to the cathode 106 through the proton exchange membrane 102. In a simplified single fuel cell, the electrons released at the anode 104 are preferably conducted through an external circuit (not shown) connected to the cathode 106 which creates a current, as will be discussed in greater detail below.
The proton exchange membrane (PEM) 102 is a cation permeable, solid polymeric proton conductive recast ionomer membrane or sheet, having H+ ions as the mobile ion, which are well known in the art. One broad class of cation exchange proton conductive resins is the so-called sulfonic acid cation exchange resin. These ion exchange membranes or sheets are well known in the art. The preferred membranes 102 are perfluorinated sulfonic acid polymer electrolyte membranes, commercially available under the trade name Nafion® sold by E.I. DuPont de Nemours & Co. Other similar membranes are sold by Asahi Glass and Asahi Chemical Company.
As best shown in
With general reference to
Further, another advantage of the present invention relates to water management of the fuel cell. Typically, product water is generated in the fuel cell reaction and rejected at the cathode 106 where the water typically escapes by simple flow or by evaporation. However, means may be provided if desired, for collecting the water as it is formed to carry it away from the fuel cell 99. Good water management in the cell enables successful long-term operation of electrochemical fuel cell 99. Spatial variations of water content within the membrane 102 of a current-carrying fuel cell result from the electro-osmotic dragging of water with proton (H+) transport from anode 104 to cathode 106, the production of water by the oxygen reduction reaction at the cathode 104, humidification conditions of the inlet gas stream, and “back-diffusion” of water from cathode 106 to anode 104. It should be noted that for currently employed PEM membranes 102, preferred operational conditions to achieve optimum efficiency include a cathode 106 outlet relative humidity of 100% or greater. Previously, to achieve this humidity, both the anode 104 and cathode 106 reactant streams were externally humidified prior to entering the fuel cell 99, which necessitated humidification equipment. As will be discussed in greater detail below, one advantage of the present invention is a reduction and/or elimination of the need for external humidification of the cathode 106 and/or anode 104 inlet stream.
According to the present invention, the porous fluid distribution media 107 comprises an electrically conductive non-metallic composition. First external surfaces 170 of the fluid distribution media 107 refers to those surfaces (i.e., surfaces 126,130) of the first and second fluid distribution media layers 120,122 which contact the substrate element sheets 132,134. Second external surfaces 172 (i.e., 124,128) of the fluid distribution media 120,122 are exposed to major surfaces 174 of the MEA 100. As used herein, “major surface” refers to a surface of an element having a greater dimension or surface area than other surfaces of the element, for example, an element that has an aspect ratio of greater width to height, where the surface area of the side corresponding to the element's height (e.g., thickness) is significantly smaller than the surface area of the width of the same element.
The fluid distribution media 107 is preferably highly porous (i.e. about 60%-80%), having a plurality of pores 176 formed within a body 178 of the fluid distribution media 107. “About” when applied to values indicates that the calculation or the measurement allows some slight imprecision in the value (e.g., with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If, for some reason, the imprecision provided by “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates a possible variation of up to 5% in the value. The plurality of pores 176 comprise a plurality of internal pores 180 and external pores 182 that are open to one another and form continuous flow paths or channels 184 throughout the body 178 that extend from a first external surface 170 to the second external surface 172 of the fluid distribution media 107. Internal pores 180 are located within the bulk or body 178 of the fluid distribution media 107 and external pores 182 end at the distribution media layer 107 surface, for example, 170 or 172. As used herein, the terms “pore” and “pores” refers to pores of various sizes, including so-called “macropores” (pores greater than 50 nm diameter), “mesopores” (pores having diameter between 2 nm and 50 nm), and “micropores” (pores less than 2 nm diameter), unless otherwise indicated, and “pore size” refers to an average or median value including both the internal and external pore diameter sizes. It is preferred that the average pore size be equivalent to a radius of greater than about 2 μm and less than about 30 μm. Since these openings are disposed internally within the body 178 of fluid distribution media layers 107 (e.g. 120,122) the surfaces of the openings are referred to as internal surfaces 186, or the media interior.
According to the present invention, preferred non-metallic conductive fluid distribution media 107 comprises carbon. Such fluid distribution media 107 is well known in the art, and preferably comprises carbon fiber or graphite. The porous fluid distribution media 107 may be manufactured as paper, woven cloth, non-woven cloth, fiber, or foam. One such known porous fluid distribution media 107 comprises a graphite paper having a porosity of about 70% by volume, an uncompressed thickness of about 0.17 mm, which is commercially available from the Toray Company under the trade name Toray TGPH-060. In preferred fuel cell assemblies, Toray TGPH-060 is used on the anode side 104. Another preferred porous fluid distribution media 107 has about 70% by volume porosity, and is 0.26 mm thick, commercially available under the trade name TGPH-090, by Toray Company. It is preferred that such a fluid distribution media 107 is pretreated by grinding the side facing the MEA 100 to a final thickness of 0.17 mm, where it is placed on the cathode side 106. Reactant fluids are delivered to the MEA 100 via the fluid flow channels 184 within the first and second porous media layers 120,122, where the electrochemical reactions occur and generate electrical current.
Preferred materials of construction for the separator plate substrates 132,134 include conductive metals, such as stainless steel, aluminum, and titanium, for example. In preferred embodiments, the separator element 132,134 material is electrically conductive, and may form metal oxides when subjected to oxygen. The most preferred materials of construction for the separator plate substrates 132,134 are higher grades of stainless steel that exhibit high resistance to corrosion in the fuel cell, such as, for example, 316L, 317L, 256 SMO, carpenter 20, Inconel 601, Alloy 276, and Alloy 904L.
Electrical contact through an electrically conductive path at the contact regions 129 is dependent upon the relative electrical contact resistance at an interface of the surfaces (e.g., 172 to 174) of the contacting elements (107 and 103). Although non-metallic fluid distribution media 107 is preferred for its corrosion resistance, strength, physical durability in a fuel cell environment, and low bulk electrical resistance, it has been found that the interface between non-metal fluid distribution media 107 with either the electrodes 103 or metal substrates 132,134 can contribute to an increased electrical contact resistance at the interface due to the dissimilarity of the respective materials. For example, it is believed that the molecular interaction between a metal (e.g., substrate surface 138,140 or catalyst particles 152 in the electrode) and non-metal materials at such interfaces may increase the contact resistance due to differences in the respective surface energies and other molecular and physical interactions. In particular, the present invention provides a reduced electrical resistance (i.e., increased electrical conductivity and hence increased electron transfer) from the interface of the electrode surface 174 to the fluid distribution media layer 107 surface 172 as compared to an electrical resistance of a comparative porous media constructed of the same material but having non-metallized electrical contact regions with a similar MEA. In alternate preferred embodiments, the present invention further provides an overall reduction in the electrical resistance of the fuel cell assembly, by reducing the overall electrical resistance of the several assembled components of the fuel 99 cell via reduced resistance at interfaces with both surfaces 170,172 of the fluid distribution media layers 107 confronting the MEA 100 and separator element substrates 132,134, respectively.
Thus, the present invention provides a conductive metal coated on the outer surfaces 181 of the pores 176 of the porous non-metallic fluid distribution media 107 to form metallized regions 188. The metallized regions 188 are formed along the second external surfaces 172 of the porous media layer 107 that confront the major surfaces 174 of the MEA electrodes 103. The metallized regions 188 integrated with the fluid distribution media layer 107 at the second external surface 172 have been demonstrated to sustainedly reduce contact resistance when compared with fluid distribution media layers having no metal coating or metallized regions. It is preferred that the contact resistance at the interface of the electrodes 103 with the metallized regions 188 of electrically conductive fluid distribution element 107 of the present invention is less than 30 mOhm-cm2 and more preferably less than 15 mOhm-cm2. Although not limiting to the manner in which the present operation operates, it is believed that the conductive metallized regions 188 at the contact surface 172 of the fluid distribution media 107 provide an improved electrical interface at the contact regions 129 by providing a more electrically conductive interface (via the metallized regions 188) and further may be impacted by contacting more similar materials (i.e. catalyst metals 152) with correspondingly similar molecular and physical characteristics (e.g. surface energies). Thus, the present invention provides enhanced electrical conductivity, and consequently may allow for the ability to lower catalyst 152 loading in the electrodes 103 by such improved electrical conductivity, hence reducing fabrication cost for the fuel cell assembly 99.
In one preferred embodiment according to the present invention, the metallized regions 188 are ultra-thin and applied along the second external surface 172 of the fluid distribution media 107. “Ultra-thin” layers of conductive metal deposited within the metallized regions 188 generally refers to thicknesses less than about 40 nm, and most preferably less than 15 nm. The thickness of the metallized regions 188 is preferably less than about 10 nm, more preferably from between about 2 to about 10 nm, and most preferably between about 5 to about 10 nm along the surface 172 adjacent to the electrodes 103 of the MEA 100. It has been found experimentally that optimal water management (where sufficient water is retained to permit humidification of the membrane 102, while not flooding the electrodes 103) corresponds in certain embodiments to those where the metallized region 188 thickness on porous media layers 107 along the cathode side 106 of the MEA 100 is between about 5 to about 10 nm.
It is preferred that the metallized regions 188 are electrically conductive, oxidation resistant, and acid-resistant and in certain preferred embodiments the electrically conductive metal forming the metallized region comprises a compound containing a noble metal, selected from the group consisting of: ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), iridium (Ir), platinum (Pt), osmium (Os), and mixtures thereof. Such compounds may comprise elemental forms of the conductive metal, or may comprise conductive compounds of metal nitrides, metal oxides, and metal carbides. Other preferred metals for the metallized regions 188 include those that comprise chromium (Cr), titanium (Ti), or tin (Sn). Electrically conductive compounds comprising such metals include, by way of example, chromium nitride (CrN), doped-tin oxide (SnO), and doped titanium oxide (TiO). A most preferred conductive metal for the metallized regions 188 comprises gold (Au). As recognized by one of skill in the art, the conductive metal composition may comprise mixtures of the above identified metals.
In the embodiment shown in
In an alternate preferred embodiment, where the first external surface 170 comprises metallized regions 190, it is preferred that the thickness of the metallized regions is less than 80 nm, preferably less than 50 nm, and most preferably between about 2 to about 10 nm. In certain preferred embodiments of the present invention, the thickness of the metallized regions 190 is less than or equal to the depth of two atomic monolayers of the metal selected for the coating 190. As will be described in greater detail below, the preferred thicknesses of the respective metallized regions 188,190, may differ depending on the application, and desired thicknesses are related to both electrical conductivity and desired fuel cell operating conditions, including water management. However, the electrically conductive metal of the metallized regions 190 is preferably selected from the same compositions described above for the metallized regions 188. Likewise, the conductive metals of metallized regions 188 and 190 may be independently selected from one another, or may comprise the same composition, including the same electrically conductive metal(s).
It is preferred that the conductive metallized regions 188,190 coat the external pore 182 outer surfaces 181 and the surfaces 186 of the internal pores 180 and extends into the body 178 of the fluid distribution media 107 at a depth of at least about 2 to about 10 nm from respective surfaces 170 or 172.
The first surface 170 a of the fluid distribution media 107 a comprises discrete metallized regions 190 a of the porous media 107 a which correspond to electrically conductive contact regions 144 of the external surface 170, and the non-metallized regions 194 correspond to the electrically non-conductive regions. Electrically conductive regions 190 a include those areas that contact lands 136 and establish the electrically conductive path at the contact regions 144. In previously described embodiments, such as that in
A variety of depositing methods may be employed to apply the conductive metal compositions that form the metallized regions (e.g., 188,190, 190 a) of the fluid distribution media 107. One preferred method of depositing the conductive metal of the metallized regions 188,190 onto the fluid distribution porous media 107 will now be described with reference to
Another preferred PVD method that is also suitable for the present invention, while not shown, is magnetron sputtering, where a metal target (the conductive metal for the metallized regions 188,190,190 a) is bombarded with a sputter gun in an argon ion atmosphere, while the substrate is charged. The sputter gun forms a plasma of metal particles and argon ions that transfer by momentum to coat the substrate. Other preferred methods of applying a metal coating 188,190,190 a according to the present invention include electron beam evaporation, where the substrate is contained in a vacuum chamber (from between about 10−3 to 10−4 Torr or about 1.3×10−1 Pa to 1.3×10−2 Pa) and a metal evaporant is heated by a charged electron beam, where it evaporates and then condenses on the target substrate. The conductive metal of the metallized regions 188,190,190 a may also be applied by electroplating (e.g. electrolytic deposition), electroless plating, chemical vapor or pulse laser deposition.
Preferred embodiments of the present invention provide a low contact resistance across the separator plate substrates 132,134 through the porous media 107 having the metallized regions 188,190,190 a to the MEA 100. It is preferred that the contact resistance across an entire fuel cell (from separator plate to separator plate) is less than 100 mOhm/cm2 (mOhm/cm2) and more preferably less than 80 mΩ/cm2 where the fuel cell is under compressive force. Further, electrically conductive substrate elements 132,134 according to certain preferred embodiments of the present invention do not require the removal of a passivation layer (i.e. metal oxide layer) from the metallic separator plate substrates 132,134 along contact surfaces 138,140 prior to their incorporation into the fuel cell assemblies (for example, 99,101,111) of the present invention. Generally, a metal substrate 132,134 having an oxide layer that contacts a non-metallic fluid distribution layer (without metallized regions 190) creates an impermissibly high electrical contact resistance. Thus, prior art methods of removing the oxide layer include a variety of methods, such as cathodic electrolytic cleaning, mechanical abrasion, cleaning the substrate with alkaline cleaners, and etching with acidic solvents or pickle liquors. Eliminating the necessity for removing the metal oxides from the contact surfaces 138,140 of the metallic separator plate 132,134 is thus optional in accordance with the certain preferred embodiments of the present invention.
Thus, one preferred aspect of the present invention includes employing the separator element substrate 132,134 comprising stainless steel, where the substrate surface 132,134 does not require the extensive removal of a passivation layer from the contact surface 138,140, such as disclosed in commonly assigned U.S. patent application Ser. No. 10/704,015 filed on Nov. 7, 2003. The improved electrical conductivity at the interface at the contact regions 144 provided by the metallized region coating 190 on the porous media 107 permits use of metals in the separator element substrates 132,134 that have a naturally occurring oxide layer at the contact surface 138,140. Hence, the present invention eliminates or significantly simplifies the costly and time intensive pre-processing step of removing some or substantially all of the metal oxides from the contact surface 138,140 of the metal substrates 132,134. Further, higher grades of stainless steel previously discussed have a high corrosion resistance, and thus can be used without any further protective treatment due to their ability to withstand the corrosive environment within the fuel cell.
The present invention is also suitable for use with separator plate element substrates 132,134 that are coated with electrically conductive protective coatings that provide corrosion resistance to the underlying metal substrate 132,134. Such coatings may comprise oxidation and corrosion resistant metal coating 190 layers (e.g. Au, Ag, Pt, Pd, Ru, Rh, Ir, Os, and mixtures thereof) or corrosion resistant electrically conductive polymeric matrices, which generally comprise oxidation resistant polymers dispersed in a matrix of electrically conductive corrosion resistant particles, as are known in the art. The protective coatings preferably have a resistivity less than about 50 ohm-cm (Ω-cm) and comprise a plurality of oxidation-resistant, acid-insoluble, conductive particles (i.e. less than about 50 microns) dispersed throughout an acid-resistant, oxidation-resistant polymer matrix, where the polymer binds the particles together and holds them on the surface 138,140 of the metal substrate 132,134. The coating contains sufficient conductive filler particles to produce a resistivity no greater than about 50 μohm-cm, and has a thickness between about 5 μm and about 75 μm depending on the composition, resistivity and integrity of the coating. Cross-linked polymers are preferred for producing impermeable coatings which protect the underlying metal substrate surface from permeation of corrosive agents.
Preferably, the conductive filler particles are selected from the group consisting of gold, platinum, graphite, carbon, nickel, conductive metal borides, nitrides and carbides (e.g. titanium nitride, titanium carbide, titanium diboride), titanium alloyed with chromium and/or nickel, palladium, niobium, rhodium, rare earth metals, and other nobel metals. Most preferably, the particles will comprise carbon or graphite (i.e. hexagonally crystallized carbon). The particles comprise varying weight percentages of the coating depending on the density and conductivity of the particles (i.e., particles having a high conductivity and low density can be used in lower weight percentages). Carbon/graphite containing coatings will typically contain 25 percent by weight carbon/graphite particles. The polymer matrix comprises any water-insoluble polymer that can be formed into a thin adherent film and that can withstand the hostile oxidative and acidic environment of the fuel cell. Hence, such polymers, as epoxies, polyamide-imides, polyether-imides, polyphenols, fluoro-elastomers (e.g., polyvinylidene flouride), polyesters, phenoxy-phenolics, epoxide-phenolics, acrylics, and urethanes, inter alia are seen to be useful with the present invention. In such an embodiment, where the surfaces 138,140 are overlaid with a protective coating, the metal substrates 132,134 comprise a corrosion-susceptible metal such as aluminum, titanium, or lower grade stainless steel that is coated with a corrosion resistant protective coating.
In certain embodiments of the present invention, it is preferred that the contact surfaces 138,140 of the separator element metal substrates 132,134 are essentially clean, where loosely adhered contaminants are removed, prior to incorporation into the electrically conductive element. Such cleaning typically serves to remove any loosely adhered contaminants, such as oils, grease, waxy solids, particles (including metallic particles, carbon particles, dust, and dirt), silica, scale, and mixtures thereof. Many contaminants are added during the manufacturing of the metal material, and may also accumulate on the contact surface 138,140 during transport or storage. Thus, cleaning of the contact surface 138,140 of the metal substrate 132,134 is especially preferred in circumstances where the metal substrate 132,134 is soiled with contaminants. Cleaning of the metal substrate 132,134 may entail mechanical abrasion; cleaning with traditional alkaline cleaners, surfactants, mild acid washes; or ultrasonic cleaning. The choice of the appropriate cleaning process or sequence of cleaning processes is selected based upon both the nature of the contaminant and the metal.
Experimental details regarding one preferred embodiment of the present invention will now be described in detail. In certain preferred embodiments the fluid distribution media differs for the anode 104 and the cathode 106 sides. As previously described, Toray TGPH 060 is preferably used for the anode side 104, which is 0.17 mm thick, whereas the cathode side 106 distribution media is Toray TGPH 090 which is 0.26 mm thick. It is preferred that the Toray TGPH 090 is pretreated by coating the outer surface with polytetrafluouoethylene (PTFE) and then ground on one side to a final thickness of 0.17 mm. Thus, gold was deposited by ion-assisted PVD onto both types of Toray fluid distribution media graphite paper. In the first experiment, gold was deposited by PVD onto the Toray paper by a Teer magnetron sputter system. The Toray paper was introduced into the vacuum chamber and when the pressure in the vacuum chamber reached 5×10−5 the deposition of Au was done. The magnetron targets were 99.99% pure Au. The Au deposition was done at −50V bias potential using 0.25 A current for one minute to achieve a gold coating 130 thickness of 10 nm. Au was deposited at a rate of 0.16 nm/s using magnetron sputter system. The thickness of the samples was calibrated using electron probe microanalysis (EPMA). The deposition temperature was about 25° C. to about 30° C.
As shown in
The Control comprises a prior art impermeable separator plate constructed of a 317L stainless steel without any coatings or pretreatment. The fuel cell was assembled with the same Toray diffusion media for the anode and cathode side as described immediately above, however the Toray media did not have any metallized regions. Each Toray diffusion media was arranged to sandwich opposite sides of an MEA. The Toray diffusion media are each surrounded by and contacting the uncoated and untreated stainless steel plates.
The contact resistance was measured in the fuel cell using current interruption method with Scribner Associate Software. Contact resistance measurements were measured as milli-Ohm centimeter squared (mΩ·cm2) through a cycle of applied current density through a range of 100, 300, 600, 800, 1000, and 1500 mA/cm2. The fuel cell was operated with a hydrogen to air stoichiometry of 2/2 pressurized to 25 psig (approximately 175 kPa) and the anode inlet was 100% relative humidity, the cathode inlet was operated dry (approximately 0% relative humidity). The outlet humidity was measured as approximately (114%)
As can be observed from the data, the total cell resistance of Sample 1 is significantly lower than the control throughout the entire cycle of applied current. Further, the cell voltage for Sample 1 was greater throughout the experiment and substantially greater at higher applied current (600-1000 mA/cm2) corresponding to typical fuel cell operating conditions. Thus, Sample 1 of the present invention demonstrated a significant improvement in performance by exhibiting higher voltage potential and reduced resistance through all ranges of current applied, as compared to the prior art control.
Thus, the present invention provides a method for manufacturing an assembly for a fuel cell, comprising depositing an electrically conductive metal on a surface of an electrically conductive porous media to form one or more metallized regions having an ultra-thin thickness. The surface having the metallized regions is positioned adjacent to an electrode of the MEA. The electrode is contacted with the surface having the metallized regions to form an electrically conductive path between the substrate and the porous media.
One advantage of the present invention relates to improved water management. As previously discussed, optimal efficiency of the fuel cell occurs where the outlet humidity from the cathode is 100% relative humidity or greater. Maintaining sufficient water content in the fuel cell to prevent drying of the membrane has typically been a significant problem during operations, thus, the inlet streams to both the anode and cathode are humidified, usually to a target of at least 100%. It was discovered upon testing, that where the sample was prepared with metallized regions along both sides of the Toray fluid distribution media (as in Sample 1) and the fuel cell was operated to have a typical inlet humidity to the cathode of 100% relative humidity (which is a standard target for cathode inlet humidity), the fuel cell was inundated with excess water and in some circumstances flooded. Thus, in contravention to known prior art, the present invention reduces the need for external humidification of inlet reactant streams to the MEA.
A dry cathode inlet of approximately 0% relative humidity demonstrated the best performance, having a cell voltage of 0.61 V at a current density of 1.5 mA/cm2, as compared to the mere 0.5 V at 50% cathode inlet relative humidity. Thus a drop in cell performance of 200 mV was observed by increasing the cathode relative humidity from dry to 50%. The cell resistance was likewise low and remained below 80 mOhm/cm2 at a current density of 1.5 mA/cm2 for all humidity values. Throughout all of the cathode inlet humidity values, the cathode exit humidity was likewise monitored. As previously mentioned, the proton conductivity is greatest through the membrane when the cathode outlet humidity is 100% or greater. As can be seen in
In some prior art embodiments, coating the metal substrate of the bipolar plates, in particular stainless steel substrates, with a protective metal coating has created high MEA contamination, which can lead to poisoning of the catalyst (and hence catalyst inactivation) or overall deactivation of the proton conductive material in the membrane and electrodes over the lifespan of the fuel cell. However, in embodiments where the stainless steel forms a passivation layer of metal oxides, such contamination does not generally occur. Thus, one additional advantage of the present invention, is the optional use of an untreated stainless steel separator plate, which reduces MEA contamination, and thus reduces the potential of catalyst poisoning and overall inactivation of the membrane and electrodes.
The present invention provides a method of operating a fuel cell comprising positioning an electrically conductive porous media between a membrane electrode assembly (MEA) and an electrically conductive substrate. The porous media has a first surface having ultra-thin metallized regions, where the first surface faces the MEA. A second surface faces the conductive substrate. The first surface having the metallized regions is contacted with the MEA and the second surface facing the substrate forms an electrically conductive path from the substrate through the porous media to the MEA. The contacting is generally accomplished by imparting compressive force on the fuel cell in an assembled fuel cell stack. An electrochemical reaction is conducted in the MEA which generates electrons. Thus, the present method comprises conducting electrons to or from the MEA via the electrically conductive path while operating the fuel cell.
A reactant stream is introduced to a cathode side of the MEA while conducting the reaction. The reactant stream is delivered through the conductive porous media and does not require external humidification in certain embodiments. In certain preferred embodiments of the present invention, the reactant stream delivered to a cathode side of the MEA consists essentially of ambient air, and the ambient air is not intentionally humidified, or in the alternative the ambient air has a relative humidity of less than ambient conditions.
In alternate preferred embodiments, the reactant stream introduced to the cathode side of the MEA for the reaction is externally humidified prior to entry into the MEA at less than saturation conditions. In preferred embodiments of the present invention, the reactant stream introduced to a cathode side of the MEA has a water content of less than a saturation level. In alternate preferred embodiments, the second surface of the porous media further comprises one or more metallized regions comprising an electrically conductive metal for reducing electrical resistivity between the substrate and the porous media. As appreciated by one of skill in the art, the porous media according to the present invention may be arranged on both sides of the MEA.
Conductive elements prepared in accordance with the present invention provide fuel cells with highly efficient and optimized fuel cell operation. The present invention provides an improved electrical interface between the non-metallic porous fluid distribution media and the electrodes of the MEA, which reduces electrical resistance and increases catalyst activity. Such increased catalyst activity can reduce the catalyst loading requirements in the electrodes of the MEA and thus reduce manufacturing expenses. Additionally, the conductive porous fluid distribution media according to the present invention improve fuel cell water management by eliminating the need for external humidification of the cathode inlet stream while maintaining adequate hydration of the membrane in the MEA.
Further, alternate preferred embodiments of the present invention likewise reduce the electrical resistance between the non-metallic porous fluid distribution media and the metallic substrate of the separator element, to provide an overall lower electrical resistance across the fuel cell. The metallized regions of the present invention provide an ultra-thin conductive metal coating that sufficiently covers the surface of the porous fluid distribution element to provide a low contact resistance for an electrically conductive fluid distribution element, which improves the overall performance of a fuel cell. Furthermore, the thickness of the metal coating is such that the manufacturing cost of preparing an electrically conductive fluid distribution element is minimized. Processing costs are further reduced by eliminating the step of removing metal oxides from metal substrates that will form an electrical interface with the fluid distribution element. The improved electrical interface reduces contact resistance and promotes more widespread and even current distribution, which will increase the operational efficiency and overall lifetime of the membrane and the fuel cell stack.
The description of the above embodiments and method is merely exemplary in nature and, thus, variations that do not depart from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention.
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|Classification coopérative||Y10T428/24999, Y10T428/249986, H01M8/0234, H01M8/0245, H01M8/0232, Y02E60/50|
|Classification européenne||H01M8/02C4C, H01M8/02C4K2, H01M8/02C4A|
|20 mai 2004||AS||Assignment|
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