Abstract:
A solid polymer electrolyte composite membrane and method of manufacturing the same. The composite membrane comprises a porous ceramic support having a top surface and a bottom surface. The porous ceramic support may be formed by laser micromachining a ceramic sheet or may be formed by electrochemically oxidizing a sheet of the base metal. A solid polymer electrolyte fills the pores of the ceramic support and preferably also covers the top and bottom surfaces of the support. Application of the solid polymer electrolyte to the porous support may take place by applying a dispersion to the support followed by a drying off of the solvent, by hot extrusion of the solid polymer electrolyte (or by hot extrusion of a precursor of the solid polymer electrolyte followed by in-situ conversion of the precursor to the solid polymer electrolyte) or by in-situ polymerization of a corresponding monomer of the solid polymer electrolyte.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS  
       [0001]     The present application claims the benefit under 35 U.S.C. 119(e) of U.S. Provisional Patent Application Ser. No. 60/614,143, filed Sep. 29,2004, the disclosure ofwhich is incorporated herein by reference. 
     
    
     BACKGROUND OF THE INVENTION  
       [0002]     The present invention relates generally to solid polymer electrolyte membranes of the type suitable for use in electrochemical devices and relates more particularly to a novel such membrane.  
         [0003]     Electrochemical devices ofthe type comprising a solid polymer electrolyte membrane (PEM) sandwiched between a pair of electrodes are well-known, such electrochemical devices finding applications as, for example, fuel cells, electrolyzers, sensors, gas concentrators, gas compressors, supercapacitors, ultracapacitors and industrial electrochemical process units.  
         [0004]     A common type of solid polymer electrolyte membrane consists of a homogeneous perfluorosulfonic acid (PFSA) polymer, said PFSA polymer being formed by the copolymerization of tetrafluoroethylene and perfluorovinylether sulfonic acid. See e.g., U.S. Pat. No. 3,282,875, inventors Connolly et al., issued Nov. 1, 1966; U.S. Pat. No. 4,470,889, inventors Ezzell et al., issued Sep. 11, 1984; U.S. Pat. No. 4,478,695, inventors Ezzell et al., issued Oct. 23, 1984; U.S. Pat. No. 6,492,431, inventor Cisar, issued Dec. 10, 2002, all of which are incorporated herein by reference. A commercial embodiment of a perfluorosulfonic acid polymer PEM is available from DuPont (Wilmington, DE) as NAFION® PFSA polymer.  
         [0005]     Although PFSA PEMs function in a generally satisfactory manner in electrochemical devices, there nonetheless remains room for improvement in certain properties of PFSA PEMs. For example, one common difficulty associated with PFSA PEMs is a lack of mechanical strength, resulting in a tendency for the PFSA PEMs to tear, especially when being handled (such as during assembly of an electrochemical cell) or in stressed areas where compression is applied thereto (such as in peripheral areas of PEMs sealed under pressure to other electrochemical cell components). Such a lack of mechanical strength also often leads to electrical shorting, which results in premature failures during cell operation as the typical porous electrodes in contact with the PEM have a tendency to penetrate the softened PEM. This problem of shorting is even greater when the membrane is made thin (e.g., less than 25 microns) in order to decrease membrane resistance.  
         [0006]     Because the tendency to tear and to short is greatest when the PFSA PEMs are wet (especially at elevated temperatures) and because the PFSA PEMs must be wet in order to function properly, one approach to this problem has been to assemble electrochemical cells with dry PEMs and then to subject the PEMs to a humidification process. This approach, however, has its own shortcomings. One such shortcoming is that the dry assembly requires special moisture-free facilities, such as a “dry room.” Another such shortcoming is that the humidification process is time-consuming. Still another such shortcoming is that the humidification process typically results in the PEM swelling in a non-uniform manner, thereby creating stress in some areas of the PEM, as well as in other components of the cell that are in contact with the PEM, and introducing irregularities in the contact pressure applied over the entire active surface area of the PEM. (When the contact pressure is not uniform over the entire active surface area of the PEM, the performance of the electrochemical cell is adversely affected.) As can readily be appreciated, such irregularities are amplified where humidification is applied to a plurality of PEM-containing fuel cells arranged in a stack.  
         [0007]     Moreover, if the PEM is subjected to variable conditions of humidity (e.g., alternating wet and dry intervals during periods of use and non-use, respectively), the membrane will undergo additional dimensional changes as it swells when wet and shrinks when dry. Such dimensional changes cause further stress to the PEM and to the other cell components, all of which are tightly packed together. If sufficiently great, such stress results in damage to the PEM and/or to the cell components in contact therewith. Pinholes/microcracks have a tendency to form along the cell or flow-field edges where one side of the membrane is heavily compressed by the fixture while the other side can still partially swell.  
         [0008]     One approach that has been taken to address the aforementioned problem of low mechanical strength of PFSA PEMs has been to cross-link the membrane polymer. Such cross-linking reduces the swelling of the membrane when wet which, in turn, reduces the deterioration of the mechanical strength of the membrane when wet. Unfortunately, however, such cross-linking tends to make the membrane undesirably brittle under dry conditions.  
         [0009]     Another approach to this problem is disclosed in U.S. Pat. No. 6,635,384, inventors Bahar et al., which issued Oct. 21, 2003, and which is incorporated herein by reference. In the aforementioned &#39;384 patent, there is described a composite membrane that comprises a microporous sheet, said microporous sheet preferably being an expanded polytetrafluoroethylene (ePTFE) membrane, said ePTFE membrane preferably being formed by stretching a sheet of polytetrafluoroethylene (PTFE) until pores are formed therein. The structure defining the pores of the microporous sheet is then at least partially covered with a functional material selected from (i) inorganic particulate; (ii) metal; and (iii) an organic polymer. In addition, the pores of the sheet are then at least partially filled with polymer electrolyte selected from (i) polymer compositions that contain metal salts; (ii) polymeric gels that contain electrolyte; and (iii) ion exchange resins, such as PFSA.  
         [0010]     One disadvantage that has been noted by the present inventors regarding the foregoing composite membrane is that the pores of the expanded polytetrafluoroethylene (ePTFE) sheet tend to follow a tortuous pathway between opposing surfaces of the ePTFE sheet, as opposed to following a direct or straight pathway between opposing surfaces. As a result of these tortuous pathways, protons conducted through the pores (by means ofthe polymer electrolyte that is disposed within the pores) have to travel considerably longer pathways through the membrane than merely the thickness of the membrane. Such longer pathways result in a reduction in the conductivity of the membrane and an increase in the resistivity of the membrane.  
         [0011]     Another disadvantage that has been noted by the present inventors regarding the foregoing composite membrane is that a microporous sheet of ePTFE possesses only slightly better mechanical strength than a PFSA PEM. Consequently, the foregoing composite membrane is not significantly stronger than a PFSA PEM and is subject to the same types of shortcomings discussed above in connection with PFSA PEMs.  
         [0012]     Still another disadvantage that has been noted by the present inventors regarding the foregoing composite membrane is that the stretching process that is used to expand the PTFE sheet to create the desired pores tends to result in a fairly uniform yet random distribution of pores throughout the sheet and cannot be tailored to control the positioning or concentration of pores in particular regions of the sheet. This is unfortunate because certain regions of the membrane, such as the membrane active area edges/corners or the membrane contact area with the current collector, are typically subjected to greater stresses than other regions. Consequently, pores in these regions of high stress undesirably diminish membrane strength in those regions where membrane strength is needed most.  
       SUMMARY OF THE INVENTION  
       [0013]     It is an object of the present invention to provide a novel solid polymer electrolyte membrane of the type that is suitable for use in electrochemical devices, such as, but not limited to, fuel cells, electrolyzers, sensors, gas concentrators, gas compressors, supercapacitors, ultracapacitors and industrial electrochemical process units.  
         [0014]     It is another object of the present invention to provide a solid polymer electrolyte membrane of the type described above that overcomes at least some of the drawbacks discussed above in connection with existing solid polymer electrolyte membranes.  
         [0015]     Therefore, according to one aspect of the invention, there is provided a solid polymer electrolyte composite membrane, said solid polymer electrolyte composite membrane comprising (a) a ceramic support, said ceramic support having opposing top and bottom surfaces and a plurality of pores extending from said top surface to said bottom surface; and (b) a first solid polymer electrolyte at least partially filling at least some of said pores.  
         [0016]     In a preferred embodiment, the ceramic support contains or is made of at least one of silica, quartz, glass, boron carbonate, silicon carbide, alumina, titania, silica tungstate, sintered valve metal oxides (e.g., tantalum or niobium oxide) and non-conductive diamond or diamond-like coatings, the support having a thickness of about 1 μm to 50 μm. A plurality of cylindrical pores are formed in the support by laser micromachining. The pores have a diameter of about 1 μm to 200 μm and are arranged in a defined pattern, such as in a uniform hexangular pattern or in a pattern in which fewer pores are located in areas of higher membrane stress and more pores are located in areas of lower membrane stress. A solid polymer electrolyte, such as PFSA polymer, fills the pores. This may be effected, for example, by filling the pores with a solution/dispersion of the solid polymer electrolyte and then drying off the solvent, by filling the pores with a precursor of the solid polymer electrolyte and then converting said precursor to said solid polymer electrolyte by base hydrolysis, or by filling the pores with a monomer of the solid polymer electrolyte and then polymerizing the monomer in-situ. Additional solid polymer electrolyte, which may be the same as or different than that filling the pores, may be applied to one or both of the top and bottom surfaces of the ceramic support.  
         [0017]     In another preferred embodiment, a porous ceramic support is prepared by the controlled electrochemical oxidation of a sheet of the base metal. The pores of such a support may have a diameter of about 0.01 micron to 100 microns and may be arranged in a honeycomb pattern. Where the pores have a diameter less than about 0.1 micron, the pores are preferably not filled using a solution/dispersion of the solid polymer electrolyte, but rather, are preferably filled using the techniques identified above involving base hydrolysis of a precursor or by in-situ polymerization.  
         [0018]     The present invention is also directed at methods of preparing a solid polymer electrolyte composite membrane. According to one aspect, said method comprises the steps of (a) providing a ceramic support, said ceramic support having a top surface and a bottom surface; (b) lasing at least one pore in said ceramic support, said at least one pore extending transversely from said top surface to said bottom surface; and (c) filling at least one of said at least one pore with a first solid polymer electrolyte.  
         [0019]     According to another aspect, said method comprises the steps of (a) providing a metal sheet; (b) electrochemically oxidizing said metal sheet to form a ceramic support having a top surface and a bottom surface, said ceramic support having at least one pore extending transversely from said top surface to said bottom surface; and (c) filling at least one of said at least one pore with a first solid polymer electrolyte.  
         [0020]     The present invention is further directed at a method of preparing a perfluorosulfonic acid polymer, said method comprising the steps of (a) providing a sulfonyl fluoride precursor of said perfluorosulfonic acid polymer; and (b) adding a weak base to said sulfonyl fluoride precursor to convert said sulfonyl fluoride precursor to said perfluorosulfonic acid polymer.  
         [0021]     The present invention is also directed to membrane electrode assemblies incorporating the above-described composite composite membranes and to electrochemical devices incorporating the above-described composite membranes, such electrochemical devices including, but not being limited to, fuel cells, electrolyzers, gas concentrators, gas compressors, sensors, supercapacitors, ultracapacitors, and industrial electrochemical process units.  
         [0022]     For purposes of the present specification and claims, it is to be understood that certain relational terms used herein, such as “above,” “below,” “top,” “bottom,” “over,” “under,” “in front of,” or “behind,” when used to denote the relative positions of two or more components of an electrochemical device are used to denote such relative positions in a particular orientation and that, in a different orientation, the relationship of said components may be reversed or otherwise altered.  
         [0023]     Additional objects, as well as features and advantages, of the present invention will be set forth in part in the description which follows, and in part will be obvious from the description or may be learned by practice of the invention. In the description, reference is made to the accompanying drawings which form a part thereof and in which is shown by way of illustration various embodiments for practicing the invention. The embodiments will be described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural changes may be made without departing from the scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is best defined by the appended claims.  
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0024]     The accompanying drawings, which are hereby incorporated into and constitute a part of this specification, illustrate various embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the drawings wherein like reference numerals represent like parts:  
         [0025]      FIG. 1  is a schematic section view of a first embodiment of a solid polymer electrolyte composite membrane constructed according to the teachings of the present invention;  
         [0026]     FIGS.  2 ( a ) and  2 ( b ) are top and perspective views, respectively, of the non-electrically-conductive support shown in  FIG. 1 ;  
         [0027]      FIG. 3  is a fragmentary top view of a non-electrically-conductive support that may be used as an alternative to the non-electrically-conductive support of FIGS.  2 ( a ) and  2 ( b );  
         [0028]      FIG. 4  is a schematic depiction of the laser micromachining technique of near-field imaging;  
         [0029]      FIG. 5  is a schematic section view of a second embodiment of a solid polymer electrolyte composite membrane constructed according to the teachings of the present invention;  
         [0030]      FIG. 6  is a schematic section view of a third embodiment of a solid polymer electrolyte composite membrane constructed according to the teachings of the present invention; and  
         [0031]      FIG. 7  is an image, taken from the top, of the non-electrically-conductive support of  FIG. 6 .  
     
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS  
       [0032]     Referring now to  FIG. 1 , there is shown a schematic section view of a first embodiment of a solid polymer electrolyte composite membrane constructed according to the teachings of the present invention, said solid polymer electrolyte composite membrane being represented generally by reference numeral  11 .  
         [0033]     Composite membrane  11  comprises a non-electrically-conductive support  13  and a solid polymer electrolyte  15 , support  13  being impregnated with solid polymer electrolyte  15 .  
         [0034]     Referring now to FIGS.  2 ( a ) and  2 ( b ), support  13  can be seen to be a generally sheet-like, unitary structure, preferably of high mechanical strength, having a top surface  17  and a bottom surface  19 . The thickness of support  13  may vary, depending upon the type of use to which membrane  11  is put and the types of pressures typically encountered by support  13  in such a use. For example, where membrane  11  is used in an electrolyzer, support  13  preferably has a thickness suitable for withstanding pressures of 2000-5000 psi. For most applications, support  13  has a thickness of about 1 μm to 50 μm, preferably about 7.5 μm to 15 μm.  
         [0035]     As noted above, support  13  is preferably a rigid member; in addition, support  13  is preferably chemically resistant to acid and water hydrolysis at elevated temperatures. Materials suitable for use as support  13  include, but are not limited to, silica, quartz, glass, boron carbonate, silicon carbide, alumina, titania, silica tungstate, sintered valve metal oxides (e.g., tantalum or niobium oxide) and non conductive diamond or diamond-like coatings. A comparison of the mechanical strength of some of the above-listed ceramics to conventional PEM materials is provided below in TABLE I.  
                             TABLE I                       Material, condition   Young&#39;s Modulus (Mpa)                                NAFION ® 112 PFSA membrane, dry 20° C.   300       NAFION ® 112 PFSA membrane, wet 80° C.   70       Polytetrafluoroethylene (PTFE)   400       SiO 2  (VYCOR)   66,000       Al 2 O 3     350,000       SiC   470,000                  
 
         [0036]     As can be seen, the ceramic materials (SiO 2 , Al 2 O 3  and SiC) are orders of magnitude stronger than PFSA and PTFE.  
         [0037]     A plurality of pores  21 , preferably cylindrical in shape, extend in a direct, i.e. straight-line, fashion from top surface  17  to bottom surface  19  of support  13 . It should be stressed that the base shape of the pore can be chosen from any two-dimensional geometric shape distributed in either regular or irregular fashion. As will be discussed further below, pores  21  are made by laser micromachining. Each pore preferably has  21  a diameter of about 1 μm to 200 μm, with pores  21  constituting about 20% to 95%, more preferably about 40% to 70%, of support  13 .  
         [0038]     The conductance of a membrane including such a porous support can be easily estimated as:  
         1   G     =       Ts     σ   *   A   *   X       +       (     T   -   Ts     )       σ   *   A             
 
 where G is the ionic conductance of the composite membrane, σ is the ionic conductivity of the solid polymer electrolyte, A is the geometric area of the composite membrane, X is the percentage of pores in the support, T is the thickness of the composite membrane and T s  is the thickness of the support. 
 
         [0039]     As can be seen from the above equation, the conductance of the composite membrane is inversely proportional to the percentage of pores in the support. Thus, a support with 50% pores results in a composite membrane with conductance equivalent to a homogenous membrane twice as thick. To maximize the conductance of the supported membrane without a sacrifice in mechanical properties, a support with 50% pores may be fabricated.  
         [0040]     In the present embodiment, pores  21  are arranged in a uniform hexangular pattern over the entirety of support  13 , such pores  21  having, for example, a diameter of about 25 μm and a center-to-center spacing of about 40 μm. It is to be understood, however, that the present invention is not limited to the above-described pattern of pores and may encompass a variety of different patterns of pores. For example, as can be seen in  FIG. 3 , there is shown a fragmentary top view of a support  13 ′ having a plurality of pores  21 ′ that are arranged so that a lesser concentration of pores  21 ′ 0  may be found in areas of higher membrane stress (e.g., at the membrane edge  23  or in local “hot spots”  25 ) and a greater concentration of pores  21 ′ may be found elsewhere.  
         [0041]     Pores  21  (and  21 ′) are made by lasing support  13  with suitable laser light. Although either gas lasers or solid state lasers may be used to create pores  21 , gas lasers are preferred. Within the class of gas lasers, excimer lasers are preferred over CO 2  lasers. This is because excimer lasers produce laser light having a much shorter wavelength than that produced by CO 2  lasers (˜0.3 μm for an excimer laser vs. ˜10 μm for a CO 2  laser). Consequently, because of their shorter wavelengths, excimer lasers directly excite the covalent bonds of the support and decompose the support without creating as extreme high-temperature conditions as is the case with CO 2  lasers. Additionally, due to their shorter wavelengths, excimer lasers can create significantly smaller pores than can CO 2 lasers.    
         [0042]     Where a CO 2  laser is used to micromachine pores into the support, the whole laser beam is focused onto an area of the support until the irradiated area is ablated. Where an excimer laser is used, the relatively uniform beam intensity produced thereby provides an alternative approach to pore formation: near-field imaging. In near-field imaging, which is schematically depicted in  FIG. 4 , a mask having a pattern is placed in the path of the beam emitted by the excimer laser. The light transmitted through the pattern of the mask is then focused by an imaging lens onto the support, resulting in the mask pattern being projected onto the support, with a corresponding pattern of pores being formed in the support. As can readily be appreciated, near-field imaging enables various alternative patterns to be projected onto the support simply by using differently patterned masks.  
         [0043]     Referring back to  FIG. 1 , solid polymer electrolyte  15  can be seen to fill pores  21  and to cover thinly top surface  17  and bottom surface  19  of support  13 . Examples of suitable materials for use as solid polymer electrolyte  15  include (i) polymer compositions that contain metal salts; (ii) polymeric gels that contain electrolytes; and (iii) ion exchange resins. In general, if proton conductivity is required, a carboxylated, sulfonated or phosphorylated polymer is preferably used as solid polymer electrolyte  15 . If hydroxyl ions are needed, a polymer containing amino, imimo, ammonium, sulfonium, and phosphonium groups is preferably used as solid polymer electrolyte  15 . To enhance the ionic conductivity of membrane  11 , inorganic ionically-conductive materials, such as metal oxide (e.g., TiO 2 ), silicon oxide, metal phosphates (e.g., zirconium phosphate) or heteropolyacids, may be impregnated into the solid polymer electrolyte  15 .  
         [0044]     A preferred material for use as solid polymer electrolyte  15  is a perfluorosulfonic acid (PFSA) membrane, such as is commercially available from DuPont (Wilmington, Del.) as NAFION® PFSA polymer. Of the aforementioned NAFION® PFSA polymers, particularly preferred are those having an equivalent weight of 200 to 2000, even more preferably those having an equivalent weight of 500 to 1200, the optimal equivalent weight depending on the use to which membrane  11  is applied.  
         [0045]     Various techniques may be used to couple solid polymer electrolyte  15  to support  13 . One such technique involves providing the solid polymer electrolyte in the form of a solution/dispersion (e.g., NAFION® 1100 in water or isopropanol) and then coating support  13  with said solution/dispersion. Examples of suitable coating techniques include gravure coating, immersion (dip) coating, metering rod (Meyer bar) coating, slot die coating, rotary screen and air knife coating. The optimal coating technique for any particular case will depend on factors, such as instrument complexity, thickness accuracy, operation efficiency, initial investment, and the like. After the solution/dispersion is coated onto the support, the coated support is heated at about 50° C. to 100° C., preferably 80° C., for about 5 minutes to evaporate the solvent. If desired, one or more additional coatings may thereafter be applied. Said one or more additional coatings either may be of the same solution/dispersion previously applied in order to build up the thickness of the solid polymer electrolyte or may be different from the initial solution/dispersion in order to obtain a composite membrane with a multilayer electrolyte structure having desired properties. (An example of a composite membrane possessing such a multilayer structure is shown in  FIG. 5 , said composite membrane  51  comprising a support  13 , a first solid polymer electrolyte  53  and a second polymer electrolyte  55 .) After coating and drying each applied layer or after coating and drying all applied layers, the layer or layers are preferably cured by heating at a temperature greater than the glass transition temperature of the ionomer (e.g., 100° C. to 400° C., preferably 160° C. for 15 minutes). Such curing, which serves to sinter or anneal the ionomer, further enhances the mechanical properties of the membrane.  
         [0046]     If desired, mask coating technology may be used to create a composite membrane wherein the solid polymer electrolyte is confined to certain patches or regions.  
         [0047]     As an alternative to coating, the solid polymer electrolyte may be applied by spraying the polymer electrolyte solution/dispersion onto support  13 . Conventional spraying techniques may be used for this purpose. Such spraying is preferably performed at 80° C. and does not require a subsequent solvent evaporation step. Micro-spraying may be used to create solid polymer electrolyte patches on the support, such patches, if desired, being far smaller than those capable of being produced by masked coating techniques.  
         [0048]     Still another technique for incorporating the solid polymer electrolyte  15  into support  13  involves a membrane extrusion technique. Such a technique comprises providing a solid polymer electrolyte in the form of a thin membrane, stacking the thin precursor membrane on the top and/or bottom surfaces of support  13 , and then pressing the stack together at an elevated temperature, preferably above the melting point or glass transition temperature of the membrane, so that the membrane melts and is forced into pores  21 . In those instances in which the membrane does not melt upon heating, but rather, degrades upon heating, a membrane precursor may be heated and forced into the pores and thereafter may be chemically converted to the corresponding solid ionomer. For example, if one wished to fill pores  21  with a PFSA (which does not melt, but instead, degrades upon heating), one could use a PFSA precursor in which the acid groups are replaced with sulfonyl fluoride groups. In such a case, once the sulfonyl fluoride precursor has melted and has been forced into pores  21 , a base may be added to the PFSA precursor to convert the PFSA precursor into PFSA by base hydrolysis. Where support  13  is made of alumina or another ceramic material that degrades in the presence of a strong base (i.e., a base that donates an OH −  group), a Lewis base (i.e., a base that accepts an H + ), such as imidazole, is preferably used to convert the sulfonyl fluoride PFSA precursor into PFSA.  
         [0049]     Still yet another technique for incorporating the solid polymer electrolyte  15  into support  13  involves filling pores  21  with a corresponding monomer and then polymerizing the monomer in situ to form the desired solid ionomer. Such polymerization may be effected with the use of an initiator (e.g., vinyl) mixed in with the monomer or by radiation (e.g., UV radiation).  
         [0050]     Referring now to  FIG. 6 , there is shown a schematic section view of a third embodiment of a solid polymer electrolyte composite membrane constructed according to the teachings of the present invention, said solid polymer electrolyte composite membrane being represented generally by reference numeral  111 .  
         [0051]     Composite membrane  111  is similar in many respects to membrane  11 , the principle difference between the two membranes being that, whereas membrane  11  includes a ceramic support  13  whose pores  21  are formed by laser micromachining, membrane  111  includes a ceramic support  113  whose pores  121  are formed by the controlled electrochemical oxidation (i.e., pitting) of a sheet of the base metal (e.g., aluminum, titanium, etc.). A top view of support  113  is shown in  FIG. 7 . As can be seen, support  113  has a honeycomb-like arrangement of pores  121 . WHATMAN ANODISC membrane filter, which is commercially available from Whatman International (United Kingdom) and is marketed for filtration purposes, is made of alumina and may be used support  113 .  
         [0052]     Pores  121  made by pitting a sheet of the base metal may have a diameter as small as about 0.01 μm. However, it should be noted that, where the diameter of pores  121  is less than about 0.1 μm, pores  121  cannot easily be filled using a solution or dispersion of the solid ionomer. Consequently, preferred techniques for filling such small pores include the hot-extrusion and in-situ polymerization techniques described above.  
         [0053]     The total thickness of membrane  11  or  111  is preferably about 5 to 300 μm, more preferably 10 to 75 μm, with the thickness of the membrane being governed by application requirements. Generally, a water electrolyzer requires a thicker membrane due to its high differential pressure while an ultra-thin membrane is suitable for super capacitors since no dynamic pressure is involved for their operation.  
         [0054]     Membrane and electrode assemblies (MEAs) comprising the composite membrane of the present invention can be fabricated by pressing a precast Pt-supported on carbon/ionomer ink onto each side of the composite membrane. The foregoing method is typically referred to as the decal transfer method.  
         [0055]     One of the advantages of the composite membrane of the present invention is that catalyst ink can be directly coated or sprayed onto the top and bottom surfaces of the membrane. This direct coating of the catalyst ink is not practical for conventional ionomer membranes since such membranes change dimension when contacted with the ink. Since the composite membrane of the present invention has excellent dimensional stability when contacted with swelling agents, such as water or alcohols, the catalyst ink can be directly applied to the membrane.  
         [0056]     Another approach that may be used to fabricate an MEA using the composite membrane of the present invention involves a technique called “catalyst on diffusion media.” The diffusion medium of this technique is a porous electrically-conductive material, which is typically in the form of a thin sheet. Optionally, a microporous layer prepared from carbon black and a polymer binder may be applied to the diffusion medium. The catalyst is then sprayed onto the diffusion medium to form a diffusion electrode. A catalyst-loaded diffusion electrode is then pressed onto each side of the composite membrane to form a full MEA.  
         [0057]     The following examples are provided for illustrative purposes only and are in no way intended to limit the scope of the present invention:  
       EXAMPLE 1  
       [0058]     A plurality of pores were formed in a piece of 25 μm thick silica film using an excimer laser and near-field imaging. The diameter of each pore was 30 μm, and the distance between the centers of the pores was 60 μm. NAFION® PFSA solution, with an equivalent weight of 1100, was coated onto the porous film, and the product was then heated to dry off the solvent from the coated PFSA solution and to cure the PFSA polymer. The resultant composite membrane had a thickness of approximately 32 μm. The wet through-plane conductivity of the membrane was 0.05 S/cm, as compared to 0.10 S/cm for the neat ionomer.  
       EXAMPLE 2  
       [0059]     A 25 μm NAFION® precursor membrane in the sulfonyl fluoride form was pressed into a 60 μm WHATMAN ANODISC filter having a 1.0 μm pore size. Such pressing was effected at 350° C. at 300 psi for 1 hour. Conversion of the sulfonyl fluoride form of the membrane was then effected by hydrolyzing overnight with imidazole at 60° C. The resulting wet room temperature through-plane-conductivity of the membrane was 0.04 S/cm, as compared to 0.10 S/cm for the neat ionomer.  
         [0060]     The embodiments of the present invention recited herein are intended to be merely exemplary and those skilled in the art will be able to make numerous variations and modifications to it without departing from the spirit of the present invention. All such variations and modifications are intended to be within the scope of the present invention as defined by the claims appended hereto.