Patent Application
20120122011
The present invention relates to methods for making fuel cell membranes, gas diffusion media, fuel cell electrodes, and battery separators.
In battery applications, porous sheets are used as separators. Battery separators are porous sheets that are interposed between an anode and cathode in a fluid electrolyte. For example, in lithium ion batteries, lithium ions (Li+) move from the anode to the cathode during discharge. The battery separator acts to prevent physical contact between the electrodes while allowing ions to be transported. Typical prior art separators include microporous membranes and mats made from nonwoven cloth. Battery separators are ideally inert to the electrochemical reactions that occur in batteries. Therefore, various polymers have been used to form battery separators.
In the case of fuel cells, porous sheets are used as gas diffusion layers and supports for polyelectrolyte membranes. Gas diffusion layers play a multifunctional role in proton exchange membrane fuel cells. For example, gas diffusion layers act as diffusers for reactant gases traveling to the anode and the cathode layers while transporting product water to the flow field. Gas diffusion layers also conduct electrons and transfer heat generated at the membrane electrode assembly to the coolant, and act as a buffer layer between the soft membrane electrode assembly and the stiff bipolar plates. Although the present technologies for making gas diffusion layers for fuel cell applications work reasonably well, improvement in properties and cost are still desirable.
Accordingly, there is a need for improved methods for forming fuel cell membranes, diffusion media, fuel cell electrodes and battery separators.
The present invention solves one or more problems of the prior art by providing in at least one embodiment a method of forming a fibrous sheet that is useful in battery and in fuel cell applications. The method of this embodiment includes a step of providing a solution comprising a fluorinated cyclobutane polymer. The solution is electrospun onto a substrate to form a fibrous coating over a surface of the substrate. The fibrous coating is then formed into a fuel cell membrane, gas diffusion media, fuel cell electrode, or a battery separator. Electrospun polyelectrolyte nano-fibers can be created as a three-dimensional interconnected network along with a second phase in the system with improved mechanical properties. The polymer coatings can be prepared with controlled thickness and morphology by an industrially scalable process. The process can be used to make supports, polyelectrolyte membranes, diffusion media and novel catalysts for fuel cells and to make battery separators as well.
Exemplary embodiments of the present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
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 term “polymer” includes “oligomer,” “copolymer,” “terpolymer,” and the like; 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.
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In a variation of the present invention, non-ionomeric perfluorocyclobutane polymers alone, poly(perfluorocyclobutane) ionomers alone, or with rubber blends or with polysulfones and perfluorosulfonic acid polymers and the like, are electrospun onto different substrates along with additives like chemical mitigants (e.g., CeO2, MnO2, or cobalt tetramethoxyphenylporphyrin), catalysts (e.g., platinum on carbon) or catalyst precursors (e.g., platinum complexes). The morphology of ionomers can be controlled as nano-fibers, and different additives can be coated simultaneously onto those nano-fibers.
In another variation, polymer solution includes a polymer selected from the group consisting of Nafion™, polyvinylidene fluoride, sulfonated perfluorocyclobutanes, and combinations thereof. In a refinement, the polymers are blended with other material such as rubbers, fluoroelastomers, and the like.
In a variation of the present invention, the fibrous sheet is formed from an ion-conducting polymer having perfluorocyclobutyl (PFCB) moieties. Suitable polymers having cyclobutyl moieties are disclosed in U.S. Pat. Pub. No. 2007/0099054, U.S. Pat. Nos. 7,897,691 issued Mar. 1, 2011; 7,897,692 issued Mar. 1, 2011; 7,888,433 issued Feb. 15, 2011, 7,897,693 issued Mar. 1, 2011; and U.S. Pat. Pub. No. 2011/0053036, the entire disclosures of which are hereby incorporated by reference. The present invention also embraces sulfonated and unsulfonated ion-conducting polymers having perfluorocyclobutyl moieties. Such polymers are sometime referred to as sulfonated or unsulfonated PFCBs. In a variation, the ion-conducting polymer has a polymer segment comprising polymer segment 1:
E0-P1-Q1-P2 1
wherein:
Eo is a moiety that optionally has a protogenic group such as —SO2X, —PO3H2, —COX, and the like;
P1, P2 are each independently absent, —O—, —S—, —SO—, —CO—, —SO2—, —NH—, NR2—, or —R3—;
R2 is C1-25 alkyl, C1-25 aryl or C1-25 arylene;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C1-25 arylene;
X is an —OH, a halogen, an ester, or
R4 is trifluoromethyl, C1-25 alkyl, C1-25 perfluoroalkylene, C1-25 aryl, or E1 (see below); and
Q1 is a fluorinated cyclobutyl moiety.
In a variation of the present invention, the ion-conducting polymer comprises polymer segments 2 and 3:
[E1(Z1)d]-P1-Q1-P2 2
E2-P3-Q2-P4 3
wherein:
Z1 is absent or a protogenic group such as —SO2X, —PO3H2, —COX, and the like;
E1 is an aromatic containing moiety;
E2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;
X is an —OH, a halogen, an ester, or
d is the number of Z1 attached to E1;
P1, P2, P3, P4 are each independently absent, —O—, —S—, —SO—, —CO—, —SO2—, —NH—, NR2—, or —R3—;
R2 is C1-25 alkyl, C1-25 aryl, or C1-25 arylene;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C1-25 arylene;
R4 is trifluoromethyl, C1-25 alkyl, C1-25 perfluoroalkylene, C1-25 aryl, or another E1 group; and
Q1, Q2 are each independently a fluorinated cyclobutyl moiety.
In one refinement, d is equal to the number of aromatic rings in E1. In another refinement, each aromatic ring in E1 can have 0, 1, 2, 3, or 4 Z1 groups.
In another variation of the present embodiment, the ion-conducting polymer comprises segments 4 and 5:
wherein:
Z1 is absent or a protogenic group such as —SO2X, —PO3H2, —COX, and the like;
E1, E2 are each independently an aromatic-containing and/or aliphatic-containing moiety;
X is an —OH, a halogen, an ester, or
d is the number of Z1 attached to R8;
P1, P2, P3, P4 are each independently absent, —O—, —S—, —SO—, —CO—, —SO2—, —NH—, NR2—, or —R3—;
R2 is C1-25 alkyl, C1-25 aryl, or C1-25 arylene;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C1-25 arylene;
R4 is trifluoromethyl, C1-25 alkyl, C1-25 perfluoroalkylene, C1-25 aryl, or another E1 group;
R8(Z1)d is a moiety having d number of protogenic groups; and
Q1, Q2 are each independently a fluorinated cyclobutyl moiety.
In a refinement of this variation, R8 is C1-25 alkylene, C1-25 perfluoroalkylene, perfluoroalkyl ether, alkylether, or C1-25 arylene. In one refinement, d is equal to the number of aromatic rings in R8. In another refinement, each aromatic ring in R8 can have 0, 1, 2, 3, or 4 Z1 groups. In still another refinement, d is an integer from 1 to 4 on average.
In another variation of the present embodiment, the ion-conducting polymer comprises polymer segments 6 and 7:
E1(SO2X)d-P1-Q1-P2 6
E2-P3-Q2-P4 7
connected by a linking group L1 to form polymer units 8 and 9:
wherein:
Z1 is absent or a protogenic group such as —SO2X, —PO3H2, —COX, and the like;
E1 is an aromatic-containing moiety;
E2 is an unsulfonated aromatic-containing and/or aliphatic-containing moiety;
L1 is a linking group;
X is an —OH, a halogen, an ester, or
d is a number of Z1 functional groups attached to E1;
P1, P2, P3, P4 are each independently absent, —O—, —S—, —SO—, —SO2—, —CO—, —NH—, NR2—, —R3—, and
R2 is C1-25 alkyl, C1-25 aryl, or C1-25 arylene;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, or C1-25 arylene;
R4 is trifluoromethyl, C1-25 alkyl, C1-25 perfluoroalkylene, C1-25 aryl, or another E1 group;
Q1, Q2 are each independently a fluorinated cyclobutyl moiety;
i is a number representing the repetition of polymer segment 6 with i typically being from 1 to 200; and
j is a number representing the repetition of a polymer segment 7 with j typically being from 1 to 200. In one refinement, d is equal to the number of aromatic rings in E1. In another refinement, each aromatic ring in E1 can have 0, 1, 2, 3, or 4 Z1 groups.
In still another variation of the present embodiment, the ion-conducting polymer comprises polymer segments 10 and 11:
E1(Z1)d-P1-Q1-P2 10
E2(Z1)f-P3 11
wherein:
Z1 is absent or a protogenic group such as —SO2X, —PO3H2, —COX, and the like;
E1, E2 are each independently an aromatic or aliphatic-containing moiety wherein at least one of E1 and E2 includes an aromatic containing moiety substituted with Z1;
X is an —OH, a halogen, an ester, or
d is the number of Z1 functional groups attached to E1;
f is the number of Z1 functional groups attached to E2;
P1, P2, P3 are each independently absent, —O—, —S—, —SO—, —SO2—, —CO—, —NH—, NR2—, or —R3—;
R2 is C1-25 alkyl, C1-25 aryl, or C1-25 arylene;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, perfluoroalkyl ether, alkyl ether, or C1-25 arylene;
R4 is trifluoromethyl, C1-25 alkyl, C1-25 perfluoroalkylene, C1-25 aryl, or another E1 group; and
Q1 is a fluorinated cyclobutyl moiety,
with the proviso that when d is greater than zero, f is zero and when f is greater than zero, d is zero. In one refinement, d is equal to the number of aromatic rings in E1. In another refinement, each aromatic ring in E1 can have 0, 1, 2, 3, or 4 Z1 groups. In still another refinement, d is an integer from 1 to 4 on average. In one refinement, f is equal to the number of aromatic rings in E2. In another refinement, each aromatic ring in E2 can have 0, 1, 2, 3, or 4 Z1 groups. In still another refinement, f is an integer from 1 to 4 on average. In a variation, polymer segments 10 and 11 are each independently repeated 1 to 10,000 times to form respective polymer blocks that may be joined with a linking group L1 shown below.
In another variation of the present embodiment, the ion-conducting polymer comprises:
wherein:
Z1 is hydrogen or a protogenic group such as —SO2X, —PO3H2, —COX, and the like;
E1 is an aromatic containing moiety;
A is absent or oxygen (O) or a chain extender having a carbon backbone;
X is an —OH, a halogen, an ester, or
P1, P2 are each independently absent, —O—, —S—, —SO—, —SO2—, —CO—, —NH—, NR2—, or —R3—, and
R2 is C1-25 alkyl, C1-25 aryl, or C1-25 arylene;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, or C1-25 arylene;
R4 is trifluoromethyl, C1-25 alkyl, C1-25 perfluoroalkylene, C1-25 aryl, or another E1 group; and
Q1 is a fluorinated cyclobutyl moiety.
In a variation of the present embodiment, polymer segment 12 is repeated j times to form a polymer block described by formula 13.
In a refinement, j is from about 1 to 10,000. In another refinement, j is from about 2 to about 100. In another refinement, j is from about 3 to about 50. In still another refinement, j is from about 4 to about 40.
In a variation of the present invention, the polymer having polymer segment 1 includes a second polymer segment having formula 14:
E2-P3-Q2-P4 14
wherein:
E2 is an aromatic containing moiety;
P3, P4 are each independently absent, —O—, —S—, —SO—, —SO2—, —CO—, —NH—, NR2—, or —R3—, and
R2 is C1-25 alkyl, C1-25 aryl, or C1-25 arylene;
R3 is C1-25 alkylene, C1-25 perfluoroalkylene, or C1-25 arylene;
R4 is trifluoromethyl, C1-25 alkyl, C1-25 perfluoroalkylene, C1-25 aryl, or another E2 group; and
Q2 is a fluorinated cyclobutyl moiety.
In a refinement, polymer segment 14 is repeated k times to form polymer block 15:
In a refinement, k is from about 1 to about 10,000. In another refinement, k is from about 2 to about 100. In another refinement, k is from about 3 to about 50. In still another refinement, k is from about 4 to about 40.
In another variation, polymer blocks 13 and 15 are connected by a linking group L1:
In each of the formulae 1-15, E1 and E2 include one or more aromatic rings. For example, E1 and E2, include one or more of the following moieties:
Examples of L1 include the following linking groups:
where R5 is an organic group, such as an alkyl or acyl group.
Examples for Q1 and Q2 in the above formulae are:
In a particular refinement, the ion conducting polymer includes a polymer having the following formula:
wherein k is from about 10 to about 10,000. It should be appreciated that the stereochemistry about the perfluorocyclobutane ring is only representative because the orientation can be cis or trans or 1,2- or 1,3-substitution of aryloxy-groups. It should also be appreciated that polymers with pendant side chains as set forth above are important in the preparation of high-performance catalyst fibers by electrospinning a mixture of PFCB ionomer with platinum on carbon catalyst materials (e.g., Tanaka). Loadings of platinum are typically between 0.1 and 0.4 mg Pt/cm2 of surface area. These mixtures are electrospun onto membrane or carbon fiber diffusion medium and then the composite is assembled into a fuel cell as shown in
In another embodiment of the present invention, the polymeric solution includes a fluoro-elastomer or fluoro-rubber. The fluoro-elastomer may be any elastomeric material comprising fluorine atoms. The fluoro-elastomer may comprise a fluoropolymer having a glass transition temperature below about 25° C. or preferably, below 0° C. The fluoro-elastomer may exhibit an elongation at break in a tensile mode of at least 50% or preferably at least 100% at room temperature. The fluoro-elastomer is generally hydrophobic and substantially free of ionic groups. The fluoro-elastomer may be prepared by polymerizing at least one fluoro-monomer such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, vinylfluoride, vinylchloride, chlorotrifluoroethylene, perfluoromethylvinyl ether, and trifluoroethylene. The fluoro-elastomer may also be prepared by copolymerizing at least one fluoro-monomer and at least one non-fluoro-monomer such as ethylene, propylene, methyl methacrylate, ethyl acrylate, styrene and the like. The fluoro-elastomer may be prepared by free radical polymerization or anionic polymerization in bulk, emulsion, suspension and solution.
Examples of fluoro-elastomers include poly(tetrafluoroethlyene-co-ethylene), poly(vinylidene fluoride-co-hexafluoropropylene), poly(tetrafluoroethylene-co-propylene), terpolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, and terpolymer of ethylene, tetrafluoroethylene and perfluoromethylvinylether. Some of the fluoro-elastomers are commercially available from Arkema under trade name Kynar Flex® and Solvay Solexis under the trade names Solef® and Technoflon®, from 3M under the trade name Dyneon®, and from DuPont under the trade name Viton®. For example, Kynar Flex 2751 is a useful copolymer of vinylidene fluoride and hexafluoropropylene with a melting temperature between about 130° C. and 140° C. The glass transition temperature of Kynar Flex 2751 is about −40 to −44° C. The fluoro-elastomer may further comprise a curing agent to allow crosslinking reactions after being blended with an ion-conducting polymer that includes a perfluorocyclobutyl moiety.
In another variation of this embodiment, the fluorinated polymer solution includes a perfluorosulfonic acid polymer (PFSA). In a refinement, such PFSAs are a copolymer containing a polymerization unit based on a perfluorovinyl compound represented by:
CF2═CF—(OCF2CFX1)m—Or—(CF2)q—SO3H
where m represents an integer of from 0 to 3, q represents an integer of from 1 to 12, r represents 0 or 1, and X1 represents a fluorine atom or a trifluoromethyl group and a polymerization unit based on tetrafluoroethylene.
A sheet of nano-fibers of main-chain or side-chain sulfonated poly(perfluorocyclobutane) (PFCBs) homopolymers, block copolymers, or sulfonated PFCBs with Kynar blends are electrospun from DMF, DMAc, alcohol, or organic solutions at the concentration of 15-25 wt % by an electrospinning apparatus. Polymer solution is pumped out of a syringe at a predetermined speed where the needle potential is fixed at 10-14 kV and the needle-to-collector substrate distance is 8-10 cm. The electrospun mats are mechanically compacted to increase the fiber density. Nanofibers in a densified mat are welded at fiber intersection points by exposing them to the solvent vapor for 10-20 minutes. Densified and welded fiber mats are then optionally backfilled with a second polymer phase (i.e. Kynar, Nafion, etc.) to provide extra mechanical integrity or other properties, such as proton conduction.
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.
This application claims the benefit of U.S. provisional Application No. 61/413,688, filed Nov. 15, 2010, the disclosure of which is incorporated in its entirety by reference herein.
| Number | Date | Country | |
|---|---|---|---|
| 61413688 | Nov 2010 | US |
