# Patent

## Title
Co(II)tetramethoxyphenylporphyrin additive to PFSA PEMS for improved fuel cell durability

## Abstract

An ion conducting membrane for fuel cell applications includes an ion conducting polymer and a porphyrin-containing compound at least partially dispersed within the ion conducting polymer. The ion conducting membranes exhibit improved performance over membranes not incorporating such porphyrin-containing compounds.

## Background
TECHNICAL FIELD
The present invention relates to ion conducting membranes for fuel cell applications.
BACKGROUND
Fuel cells are used as an electrical power source in many applications. In particular, fuel cells are proposed for use in automobiles to replace internal combustion engines. A commonly used fuel cell design uses a solid polymer electrolyte (“SPE”) membrane or proton exchange membrane (“PEM”) to provide ion transport between the anode and cathode.
In proton exchange membrane type fuel cells, hydrogen is supplied to the anode as fuel and oxygen is supplied to the cathode as the oxidant. The oxygen can either be in pure form (O2) or air (a mixture of O2 and N2). PEM fuel cells typically have a membrane electrode assembly (“MEA”) in which a solid polymer membrane has an anode catalyst on one face, and a cathode catalyst on the opposite face. The anode and cathode layers of a typical PEM fuel cell are formed of porous conductive materials, such as woven graphite, graphitized sheets, or carbon paper to enable the fuel to disperse over the surface of the membrane facing the fuel supply electrode. Each electrode has finely divided catalyst particles (for example, platinum particles), supported on carbon particles, to promote oxidation of hydrogen at the anode and reduction of oxygen at the cathode. Protons flow from the anode through the ion conductive polymer membrane to the cathode where they combine with oxygen to form water which is discharged from the cell. Typically, the ion conductive polymer membrane includes a perfluorinated sulfonic acid (PFSA) ionomer.
The MEA is sandwiched between a pair of porous gas diffusion layers (“GDL”), which in turn are sandwiched between a pair of non-porous, electrically conductive elements or plates. The plates function as current collectors for the anode and the cathode, and contain appropriate channels and openings formed therein for distributing the fuel cell's gaseous reactants over the surface of respective anode and cathode catalysts. In order to produce electricity efficiently, the polymer electrolyte membrane of a PEM fuel cell must be thin, chemically stable, proton transmissive, non-electrically conductive and gas impermeable. In typical applications, fuel cells are provided in arrays of many individual fuel cell stacks in order to provide high levels of electrical power.
One mechanism by which ion conducting polymer membranes degrade is via loss of fluorine (i.e., fluoride emission) under open circuit voltage (OCV) and dry operating conditions at elevated temperatures. Additives to PFSA membranes are required to improve fuel cell life, increase membrane durability and reduce fluoride emissions under these conditions.
Accordingly, there is a need for improved ion conducting membranes with reduced fluoride emissions.
SUMMARY OF EXEMPLARY EMBODIMENTS OF THE INVENTION
The present invention solves one or more problems of the prior art by providing in at least one embodiment an ion conducting membrane for fuel cell applications. The ion conducting membrane of this embodiment includes an ion conducting polymer and a porphyrin-containing compound at least partially dispersed within the ion conducting polymer in a sufficient amount to reduce fluoride emissions from the membrane. Moreover, the incorporation of a porphyrin-containing compound advantageously increases membrane life while decreasing electrode voltage degradation in fuel cells operating at open circuit conditions at 95° C. and 50% relative humidity. Additional benefits include reduced cost compared with additives presently used to mitigate PFSA-fuel cell ion conducting membranes.



BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of the present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
FIG. 1 is a schematic illustration of a fuel cell that incorporates an ion conducting membrane of one or more embodiments of the invention;
FIG. 2 provides plots of the cell voltage degradation and fluoride release rate (FRR) versus time for Nafion® 1000 membrane with and without Cobalt(II)tetramethoxyphenylporphyrin; and
FIG. 3 provides plots of the relative humidity (“RH”) sweep profile for Nafion® 1000 with and without Cobalt(II)tetramethoxyphenylporphyrin.



DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventors. The Figures are not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the invention and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.
Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: percent, “parts of,” and ratio values are by weight; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
It is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
It must also be noted that, as used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
Throughout this application, where publications are referenced, the disclosures of these publications in their entireties are hereby incorporated by reference into this application to more fully describe the state of the art to which this invention pertains.
With reference to FIG. 1, a fuel cell that incorporates an ion conducting membrane of one or more embodiments of the invention is provided. PEM fuel cell 10 includes polymeric ion conductive membrane 12 disposed between cathode catalyst layer 14 and anode catalyst layer 16. Polymeric ion conductive membrane 12 includes an effective amount of stannate as set forth below. Fuel cell 10 also includes conductive plates 20, 22, gas channels 60 and 66, and gas diffusion layers 24 and 26.
In an embodiment of the present invention, an ion conducting membrane for fuel cell applications includes an ion conducting polymer and a porphyrin-containing compound at least partially dispersed within the ion conducting polymer. In a variation, the porphyrin-containing compound the porphyrin-containing compound includes a moiety having formula 1:




wherein:

R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 are each independently hydrogen, alkyl, or aryl. In a refinement, R1, R2, R3, R4, are each independently substituted or unsubstituted alkyl or phenyl. In another refinement, R1, R2, R3, R4, are each phenylmethoxy. In still another refinement, R5, R6, R7, R8, R9, R10, R11, R12 are each hydrogen. In this context, substitutions may be with halogens, methoxy, ethoxy, and the like. In addition, in the case of aryl and phenyl, substitutions may also be with alkyl groups.
In another variation of the present embodiment, the porphyrin-containing compound is present in an amount from about 0.001 to about 50 weight percent of the total weight percent of the total weight of the ion conducting membrane. In a refinement, the porphyrin-containing compound is present in an amount from about 0.1 to about 10 weight percent of the total weight percent of the total weight of the ion conducting membrane.
In still another variation of the present embodiment, the porphyrin-containing compound has formula 2:




wherein M is a metal or metal-containing moiety. Examples of suitable metals for M or for inclusion, include but are not limite do in the metal containing moiety include Co, Fe, Mg, Mn, Cu, Ni, Pd, Ru, Vn, Zn, Al, B, Si, Al, In, Pb, Ag, Sn, Ti, V, Pt, Ce, and the like. Specific examples for M include Co2+, Co3+, Fe2+, Fe3+, Mg1+, Mg2+, Mn1+, Mn2+, Mn3+, ClMn3+, HOMn3+, Cu+1, Cu2+, Ni1+, Ni2+, Pd1+, Pd2+, Ru1+, Ru2+, R4+, Vn4+, Zn1+, Zn2+, Al3+, B, Si(OH)22+, Al3+, HOIn3+, HOIn3+, Pb2+, Ag+, Sn2+, Sn4+, Ti3+, Ti4+, VO+, Pt2+, Ce3+, Ce4+.

In another variation of the present embodiment, the ion-conducting membrane further comprises a metal-containing compound having a metal (i.e., metal ion) selected from the group consisting of Ce(III), Ce(IV), Mn(II) and Mn(IV). Examples of metal-containing compounds include MnO2, Mn2O3, MnCl2, MnSO4, CeCl3, Ce2(CO3)3, CeF3, Ce2O3, CeO2, Ce(SO4)2) Ce(OSO2CF3)3, and combinations thereof. In a further refinement, the metal-containing compound is selected from the group consisting of MnO2, Mn2O3 MnCl2, MnSO4, and combinations thereof.
As set forth above, the membrane of the present invention includes an ion conducting polymer. Such polymers include sulfonated tetrafluoroethylene-based fluoropolymer-copolymers. Sometimes this class of polymers is referred to as perfluorosulfonic acid (PFSA) polymers. Specific examples of such polymers include the Nafion® line of polymers commercially available from E. I. du Pont de Nemours and Company. In another refinement, the ion conducting polymer comprises a perfluorocyclobutyl moiety. Examples of these suitable polymers are set forth in U.S. Pat. Nos. 3,282,875; 3,041,317; 3,718,627; 2,393,967; 2,559,752; 2,593,583; 3,770,567; 2,251,660; U.S. Pat. Pub. No. 20070099054; U.S. Pat. Appl. No. 12197530 filed Aug. 25, 2008; 12197537 filed Aug. 25, 2008; 12197545 filed Aug. 25, 2008; and 12197704 filed Aug. 25, 2008; the entire disclosures of which are hereby incorporated by reference.
The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and scope of the claims.
Membrane Preparation. Cobalt(II)tetramethoxyphenylporphyrin (CoTMPP) is added at 5 wt. % based on perfluorosulfonic acid (PFSA) polymer solids in 1-propanol and water (3/2 weight ratio) and is homogenized with an IKA homogenizer for about 4 minutes. The CoTMPP is soluble in the ionomer solution, which is centrifuged to remove suspended air bubbles. The blood-red supernate is coated on glass with an 8-mil coating gap, Bird applicator, and the resultant wet film is then heated at 80° C. for 1 h in air and then at 130° C. for 4 h under vacuum. The green film is floated off glass and air-dried to obtain a 16-um membrane.
The improved chemical durability is measured under open circuit voltage (OCV) using 50-cm2 membrane electrode assemblies that are sub-gasketed to 38-cm2 active areas. The electrode is a platinum on carbon slurry coated on the microporous layer of a carbon fiber diffusion media to a 0.4 mg Pt cm−2 loading on both the anode and cathode. The fuel cell, with a serpentine flow-field, is operated at 95° C. and at 50% inlet R.H at a 5/5 stoichiometry on the anode and cathode at a 0.2 A cm−2 equivalent flow and 50 kPa gauge. The OCV is monitored for 200 to 800 hours and the fluoride release rate (FRR) is measured from the analysis of outlet water to determine the percent loss of fluorine versus the total fluorine inventory of the membrane. The improved chemical durability is measured under open circuit voltage (OCV) using 50-cm2 membrane electrode assemblies that are sub-gasketed to 38-cm2 active areas. The electrode is a platinum on carbon slurry coated on the microporous layer of a carbon fiber diffusion media to a 0.4 mg Pt cm−2 loadings on both the anode and cathode. The fuel cell, with a serpentine flow-field, is operated at 95° C. and at 50% inlet R.H at a 5/5 stoichiometry of anode and cathode at 0.2 A cm−2 equivalent flow and 50 kPa gauge. The OCV is monitored for 200 to 800 hours and the fluoride release rate (FRR) is measured from the analysis of outlet water to determine the percent loss of fluorine versus the total fluorine inventory of the membrane. FIG. 2 provides plots which outline the effect of small amounts of CoTMPP to dramatically improve the OCV durability of fuel cell membranes as compared to a comparative example of Nafion 1000 baseline without the added CoTMPP. The fluoride release rate of the CoTMPP membrane is 102 lower and the degradation rate is reduced.
The fuel cell performance is measured using a 50-cm2 membrane electrode assemblies prepared by loose laying a catalyst coated diffusion medium with 0.4 mg Pt cm−2 loadings on both the anode and cathode. The fuel cell, is operated from 0 to 1.5 A/cm2 at 80° C. with 32% inlet R.H at a constant 1.5/2 stoichiometry of anode and cathode at 50 kPa gauge. The addition of CoTMPP to proton exchange membranes does not reduce the in-situ fuel cell performance as shown in FIG. 3 which outlines the achieved fuel cell performance of >0.6 V at 1.5 A/cm2 with no change in the high frequency resistance (HFR) of the membrane owing to no losses in membrane resistance.
While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.

## Claims

1. An ion conducting membrane for fuel cell applications, the ion conducting membrane comprising:
an ion conducting polymer including a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer; and
a porphyrin-containing compound, wherein the porphyrin-containing compound includes a moiety having formula 1:





wherein:
R1, R2, R3, R4 are each independently phenylmethoxy and R5, R6, R7, R8, R9, R10, R11, R12 are each independently hydrogen, alkyl, or aryl.

2. The ion conducting membrane of claim 1 wherein R1, R2, R3, R4, are each independently substituted or unsubstituted alkyl or phenyl.

3. The ion conducting membrane of claim 1 wherein R5, R6, R7, R8, R9, R10, R11, R12 are each hydrogen.

4. The ion conducting membrane of claim 1 wherein the porphyrin-containing compound has formula 2:




wherein M is Co2+, Co3+, Fe2+, Fe3+, Mg1+, Mg2+, Mn1+, Mn2+, Mn3+, ClMn3+, HOMn3+, Cu+1, Cu2+,Ni1+, Ni2+, Pd1+, Pd2+, Ru1+, Ru2+, Ru4+, Vn4+, Zn1+, Zn2+, Al3+, B, Si(OH)22+, Al3+, HOIn3+, HOIn3+, Pb2+, Ag+, Sn2+, Sn4+, Ti3+, Ti4+, VO+, Pt2+, Ce3+, or Ce4+.

5. The ion conducting membrane of claim 1 wherein the porphyrin-containing compound is Co(II)tetramethoxyphenylporphyrin.

6. The ion conducting membrane of claim 1 wherein the sulfonated tetrafluoroethylene-based fluoropolymer-copolymer includes a perfluorocyclobutyl moiety.

7. The ion conducting membrane of claim 1 wherein the porphyrin-containing compound is present in an amount from about 0.001 to 50 weight percent of the total weight of the ion conducting membrane.