EP1665438A1 - Composite polymer electrolytes for proton exchange membrane fuel cells - Google Patents

Abstract

Thin films of inexpensive composite polymer electrolyte membranes containing inorganic cation exchange materials including various clay based fillers are fabricated by solution casting. The membranes exhibit higher ion exchange capacity, proton conductivity and/or lower gas crossover. In general, the composite membranes exhibit excellent physicochemical properties and superior fuel cell performance in hydrogen oxygen fuel cells.

Description

COMPOSITE POLYMER ELECTROLYTES FOR PROTON EXCHANGE MEMBRANE FUEL CELLS

CROSS REFERENCE TO EARLIER APPLICATION This application is a PCT Patent Application claiming priority of earlier-filed U.S. Patent Application Serial No. 10/644,227, entitled "COMPOSITE POLYMER ELECTROLYTES FOR PROTON EXCHANGE MEMBRANE FUEL CELLS" filed August 19, 2003, which is a CIP of the earlier filed U.S. Patent Application Serial No. 10/219,083, filed August 13, 2002, now U.S. Patent No. 6,630,265, entitled "COMPOSITE ELECTROLYTE FOR FUEL CELLS." In addition, this PCT Patent Application is a CIP of and claims the benefit of an earlier- filed PCT Application Serial No. PCT/US02/39104, entitled "COMPOSITE ELECTROLYTE FOR FUEL CELLS" filed December 5, 2002, which, in turn, claims priority from the earlier-filed U.S. Patent Application Serial No.10/219,083 entitled "COMPOSITE ELECTROLYTE FOR FUEL CELLS."

FIELD OF THE INVENTION The present invention relates to proton conducting composite polymer membranes providing one or more of the following: a functionalized polymer and one or more clay based cation exchange material. The composite polymer membranes can be used as proton conducting electrolytes in hydrogen oxygen fuel cells, proton exchange fuel cells (PEMFC) or direct methanol fuel cells (DMFC). These composite polymer membranes exhibit improvement in ion exchange capacity (IEC), proton conductivity, water uptake, oxidative resistance, thermal stability and mechanical strength.

BACKGROUND OF THE INVENTION There is a commercial trend to develop alternative energy resources that are more enduring and cheaper than current mainstream technologies. This movement is important in light of the increasing demand for energy and the gradual depletion of global fossil fuels. Fuel cells have been long considered a promising solution for the production of clean and efficient energy. The electrochemical conversion that takes place in fuel cells is not limited by the Carnot efficiency which restricts the efficiencies of internal combustion engines (ICE). A fuel cell is two or three times more efficient than ICEs converting fuel to power. Compared to batteries, fuel cells offer the advantage of continuous power as long as the reactant fuel and oxidant are supplied. This eliminates the time consuming procedure of recharging. Furthermore, fuel cells are environmentally friendly. As fuel such as hydrogen is fed into the anode compartment, a metal catalyst oxidizes the hydrogen gas into protons and electrons . Then, water is the only emission when hydrogen is used as the fuel. In fuel cells, the electrode assemblies of both the anode and the cathode contain a metal catalyst (e.g., platinum) supported by a conductive material. Some PEM fuel cells use a diffusion layer on both electrodes to help distribute gases evenly across the electrode surfaces. Fuel cells use an electrolyte between the cathode (positive electrode) and the anode (negative electrode). Fuel cells employing proton conducting electrolyte membranes are referred to as "proton exchange membrane fuel cells" (PEMFC). Reactions take place where the electrolyte, gas, and an electrode are in contact with one another (multiphase boundary). The protons are transferred through the electrolyte material to the cathode, while the electrons are conducted via an electrically conductive material through an external circuit (from the anode) to the cathode. At the cathode, an oxidant such as oxygen diffuses through the electrode where it reacts with the electrons and protons to form water. The operation of PEM fuel cells produces electricity, water, and heat. In addition to using hydrogen as a fuel, or materials that reform to hydrogen, PEM fuel cells can also operate with fuels such as methanol. In this case, methanol is introduced directly onto the anode compartment and is internally reformed. These types of fuel cells are called direct methanol fuel cells (DMFC). Among the various types of fuel cells, PEMFC and DMFC are the preferred power sources for residential, portable, and transport applications, due to their relatively lower operation temperature. Both PEMFCs and DMFCs use a proton conducting membrane as the electrolyte and composite electrode assemblies consisting of platinum based electrocatalysts and carbon. The main difference between PEMFCs and DMFCs is the type of fuel each of them uses and their emissions. While PEMFC uses gaseous hydrogen as fuel and emits only water, DMFC uses methanol as fuel and emits water and carbon dioxide. A most significant component of PEMFCs and DMFCs is the proton exchange membrane (PEM). As noted, proton exchange membranes act as an ionic conductor between anode and cathode and also separate the fuel and oxidant. Several polymer electrolyte membranes are being explored as proton exchange membranes in PEM fuel cells. Presently, both PEMFC and DMFC use expensive hydrated perfluorosulfomc acid based membranes as the electrolyte due to their excellent chemical, mechanical and thermal stability and relatively high proton conductivity of around 0.08 Scm^"1 in the hydrated state. The leading commercial membrane of this type is Nafion® (Nafion® is a trademark of

E. I. DU PONT DE NEMOURS and Company Corporation, Delaware). Nafion^® , which is described, for example, in U.S. Patent No. 4,330,654 is fabricated by melting tetrafuoroethylene and perfluorovinyl ethersulfonyl fluoride together, shaping the mixture, and then hydrolyzing the melt to yield the ionic sulfonate form. While perfluorinated ionomer membranes, such as Nafion^® membranes, are effective in PEM fuel cells they have limitations. Among these limitations are high osmotic swelling, high methanol permeability, reduced proton conductivity at elevated temperatures (> 80°C), and high cost. In particular, these membranes need to be humidified adequately to provide satisfactory proton conductivity. This is due to the hydrophilic nature of the sulfonic acid groups attached to the polymer backbone and the necessity to hydrate the ionic clusters. However, when the membrane temperature exceeds the boiling point of water, the membrane dehydrates and experiences a dramatic decrease in the proton conductivity. Consequently, perfluorinated ionomer membranes, such as Nafion® membranes, are not regarded as suitable for fuel cell applications above 100 °C. Then again, operation of the PEMFC at elevated temperatures (T > 100 °C) can provide several important advantages. For example, the higher operating temperature can provide faster reaction kinetics and better efficiency, reduce or eliminate the poisoning of the Pt-based catalysts by carbon monoxide impurity in the fuel, and possibly allow the use of less expensive non-platinum alloy or transition metal oxide catalysts. When used in DMFCs, high methanol permeability is another significant deficiency exhibited by perfluorinated ionomer membranes (e.g., Nafion® membranes). Methanol crossover is much more prevalent than hydrogen crossover, especially at concentrations above 10 wt%. This is primarily due to the liquid concentration gradient. To minimize crossover, some researchers have incorporated additives into Nafion® or vaporized methanol before introducing it to the anode side of the cell. However, this solution does not address Nafion' s® expensive cost or inherent disposition to methanol crossover. One of the other major drawbacks of perflouronated membranes such as Nafion® is high cost ($700 per square meter at the time of this writing). Due to its relatively complicated and time-consuming manufacturing process, Nafion^® is indeed very expensive. A square meter of Nafion^® is known to cost approximately $700. Typically, Nafion® membranes represent 10 to 15% of the total cost of a single PEM fuel cell or stack of fuel cells. It is generally accepted that if Nafion^® were to continue to represent the leading membrane candidate for PEM fuel cells, its cost must come down substantially before these cells can become competitive in the fuel cell market.

As noted before, Nafion® is also limited to operating temperatures below 90°C. High temperatures lead to lower proton conductivity due to dehydration and degradation. There are several studies in the literature on using sol-gel and other processes to infiltrate the porous structure of Nafion® with components that will increase its performance at elevated temperatures. Staiti et al and Tazi et al impregnated Nafion® with phosphotungstic acid and silicotungstic acid/thiophene, respectively, which increased proton conductivity and hydration levels at temperatures up to 120 °C. (See, P. Staiti, "Proton Conductive Membranes Based on Silicotungstic Acid/Silica and Polybenzimidazole", Materials Letters, 47 (2001) 241 - 246, and B. Tazi et al, "Parameters of PEM Fuel Cells Based on New Membranes Fabricated From Nafion®, Silicotungstic Acid and Thiophene", Electrochimica Ada, 45 (2000) 4329-4339). Others including P. Costamagna et al and Park et al demonstrated that Nafion® doped with zirconium hydrogen phosphate provided similar results. (See, P. Costamagna et al, "Nafion® 115/Zirconium Phosphate Composite Membranes for Operation of PEMFCs Above 100°C, Electrochimica Ada, 47, 2002, 1023 - 1033 and Y. Park et al, "Proton Exchange Nanocomposite Membranes Based on 3-Glycidoxypropyltrimethoxysilane, Silicotungstic Acid and Zirconium Phosphate Hydrate", Solid State Ionics, 145, 2001 , 149 - 160). However, by using Nafion® as the base material, these membranes are still very expensive. In addition, these additives tend to leach out of the membrane structure during fuel cell operations, which limits their utility. A variety of alternative membranes have been considered for solving the technical limitations of Nafion® in PEM fuel cells, but none of these alternatives has demonstrated sufficient advantages to replace Nafion® as the membrane of choice. One alternative membrane incorporates Nafion® or a Nafion®-like polymer into a porous polytetrafluoroethylene (Teflon®) structure. These membranes are available under the trade name Gore-Select® from W. L. Gore & Associates, Inc. and they are described in U.S. Patent Nos. 5,635,041, 5,547,551 and 5,599,614. Other alternative membranes are available under the trade names Aciplex® from Asahi Chemical Co. and Flemion® from Asahi Glass. Due to their polyfluorinated structures, these alternative membranes exhibit many of the same deficiencies as Nafion®, namely, limited ionic conductivity at elevated temperatures, dehydration or drying up, and fuel crossover. Composite ion exchange membranes with a low expansion, durable polymer impregnated with a high proton conductive polymer described, for example, in U.S. Patent No. 6,248,469, represent another alternative. The main disadvantage of such membranes is that they loose some of the cross sectional area of the proton conductive material due to the presence of the inactive support. Another alternative to Nafion® membrane employs polybenzimidazole polymers (PBI) that are infiltrated with phosphoric acid. These have been used as ion exchange membranes in PEM fuel cells and are described in U.S. Patent Nos. 5,716,727 and 6,099,988. These membranes permit PEM fuel cells to operate at higher temperatures above 130 °C, and exhibit lower osmotic expansion than that of Nafion®. However, the concentrated acid leaches out from the PBI pores as water is produced during the electrochemical fuel cell process, thereby dramatically reducing the proton conductivity and electrochemical performance with time. The leached phosphoric acid may also react with other components in the fuel cell stack. Finally, more recent research has led to unique formulations and designs of ion exchange membranes. For example, Chen et al showed that incorporation of montmorillonite and lithium triflate into poly(ethylene oxide) (PEO) enhanced the ionic conductivity of the electrolyte by nearly 16 times compared to unmodified PEO. See Chen et al, "The Novel Polymer Electrolyte Nanocomposite Composed of poly(ethylene oxide), lithium triflate and mineral clay", Polymer, 42 (2001) 9763 - 9769. However, the increased proton conductivity values in these fuel cells were still substantially lower than that produced by fuel cells using Nafion®. Similarly, Aranda et al created a membrane by combining poly(ethylene oxide) and ammonium exchanged montmorillonite, but the membrane also exhibited low ion conductivity. Based on the foregoing, there is a need for developing alternate inexpensive and higher performing proton exchange membranes. There is a further need for a membrane fabrication method that is cost effective.

SUMMARY OF THE INVENTION

The present invention is based, in part, on the discovery of composite electrolyte membranes that can be used as proton exchange membranes in PEM fuel cells, and the processes for producing these membranes. One aspect of the invention is directed to a composite electrolyte for use in electrochemical fuel cell that includes: (i) an inorganic cation exchange material; (ii) a silica- based material; and (iii) a proton conducting polymer-based material. The inorganic cation exchange material comprises about 0.1 wt% to about 99 wt%, the silica-based material comprises about 0 wt% to about 70 wt%, and the proton conducting polymer-based material comprises about 0.1 wt% to 99.9 wt% of the composite electrolyte. Preferred cation exchange materials include clays, zeolites, hydrous oxides, and inorganic salts. For example, the clay includes an aluminosilicate-based exchange material selected from the group consisting of montmorillonite, kaolinite, vermiculite, smectite, hectorite, mica, bentonite, nontronite, beidellite, volkonskoite, saponite, magadite, kenyaite, zeolite, alumina, rutile. the clay is modified to make it more compatible with organic matrices, wherein a clay modification includes exfoliation which helps to separate platelets of inorganic substance. Another aspect of the invention is directed to an electrochemical fuel cell that includes: (i) an anode; (ii) a cathode; (iii) fuel supply means for supplying fuel toward the anode; (iv) an oxidant supply means for supplying oxidant toward the cathode; and (v) a composite electrolyte positioned between the anode and cathode. The composite electrolyte includes (a) an inorganic cation material, (b) a silica-based material, and (c) a polymer-based material, wherein the inorganic cation exchange material comprises about 0.1 wt% to about 99 wt%, the silica-based material comprises about 0 wt% to about 70 wt%, and the proton conducting polymer-based material comprises about 0.1 wt% to 99.9 wt% of the composite electrolyte. Yet another aspect of the invention is directed to a method of fabricating a composite electrolyte for use in an electrochemical fuel cell. The method includes (i) applying onto a surface of a substrate a viscous liquid composition of (a) an inorganic cation exchange material, (b) silica-based material, (c) a polymer-based material, and (d) a solvent-dispersant. The method further includes (i) spreading the viscous liquid composition to form a uniform thickness layer on the substrate; and (ii) allowing the solvent to evaporate from the viscous liquid composition to yield the composite electrolyte. The inorganic cation exchange material comprises about 0.1 wt% to about 99 wt%, the silica-based material comprises about 0.1 wt% to about 70 wt%, and the polymer-based material comprises about 0.1 wt% to 99.9 wt% of the composite electrolyte.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings which, are incorporated in and constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention. Wherever convenient, the same reference numbers will be used throughout the drawings to refer to the same or like elements.

Figure 1 illustrates operation of PEM fuel cell; Figures 1A & IB show an exemplary fuel cell with an embodiment of the composite electrolyte. Figure 2 is a graph comparing IEC values of the present invention. Figure 3 is a plot of proton conductivity in saturated water vapor of the present invention Figure 4 is a plot of comparison of water retention characteristics of the present invention and Nafion®. Figure 5 is a plot of tensile strength for the present invention. Figure 6 is a plot of Young's modulus for the present invention. Figure 7 is a plot comparing proton conductivity at various temperatures for the present invention. Figure 8, is a plot comparing cell output performance for Nafion® membrane and a membrane constructed in accordance with principles of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a low cost, composite membrane and a cost effective method for fabricating such membranes. A composite membrane produced in accordance with the present invention exhibits properties comparable to Nafion® when used as an electrolyte in fuel cells. Indeed, a composite membrane provided in accordance with the present invention exhibits higher proton conductivity at elevated temperatures, greater mechanical strength, higher ion exchange capacity, and lower methanol crossover as compared to Nafion®. This composite membrane is well suited for use as a proton exchange membrane in hydrogen-oxygen fuel cells and direct methanol fuel cells. It is noted that the composite membrane can be employed as an electrolyte in conventional fuel cells which are described, for example, in U.S. Patent No. 5,248,566 and 5,5477,77. As fuel cells are modular in nature, depending on the power requirement, one can assemble them in series to make a fuel cell stack. The composite membrane is particularly suited for use as the proton exchange membrane in electrochemical fuel cells such as the one illustrated in Figure 1. The electrochemical cell 10 generally includes a membrane electrode assembly (MEA) flanked by graphite based anode 12 and cathode 16 flow field structures. The external circuit can comprise any conventional electronic device or load such as those described in U.S. Patent Nos. 5,248,566, 5,272,017, 5,547,777 and 6,387,556. The components, mainly the MEA assembly can be hermetically sealed by known techniques. In operation, fuel 18 from fuel source diffuses through the anode 12 and an oxidizer 20 from oxidant source (e.g., container or ampoule) diffuses through the cathode 16 of the MEA. The chemical reactions at the MEA develop the electromotive force and the electrons are transported though an electronic load. The composite electrolyte (the composite membrane) 22 conducts ions between the anode 12 and cathode 16, separates between the fuel 18 and oxidant 20 and insulates between the cathode and anode so that the electrons current is conducted through the external circuit rather than the membrane. Hydrogen oxygen fuel cells use hydrogen 18 as the fuel and oxygen 20 as the oxidizer. For direct methanol fuel cells, the fuel is liquid methanol. A more detailed example of a fuel cell embodying the composite electrolyte membrane is provided in Figures 1A and IB. As shown in Figure 1A, the fuel cell 10 includes a membrane electrode assembly 12 flanked by the anode and cathode structures, 36 and 38. On the anode side, the cell includes an endplate 14, graphite block or bipolar plate 18 with openings 22 to facilitate gas distribution, gasket 26, and anode carbon cloth current collector 30. On the cathode side, the cell includes stainless steel endplate 16, graphite block or bipolar plate 20 with openings 24 to facilitate gas distribution, gasket 28, and cathode carbon cloth current collector 32. The carbon cloth material is a porous conductive substance. The anode current collector 30 and cathode current collector 32 are connected to external circuit 50 by leads 31, 33 respectively. The external circuit can comprise any conventional electronic device or load such as those described in U.S. Patent Nos. 5,248,566, 5,272,017, 5,547,777, and 6,387,556. As shown in Figure IB, the membrane electrode assembly (MEA) 12 includes a proton exchange membrane 46 that is flanked by anode 42 and cathode 44 electrodes. Each electrode is made of a porous electrode material such as carbon cloth or carbon paper. The proton exchange membrane 46, fashioned as the inventive composite electrolyte, provides for ion transport during operation of the fuel cell. In operation, fuel from the fuel source 37 diffuses through the anode and an oxidizer from the oxidizer source 39 (e.g., container or ampule) diffuses through the cathode. The chemical reactions at the MEA generate electricity that is transported to the external circuit (via the anode current collector 30). Hydrogen fuel cells use hydrogen as the fuel and oxygen as the oxidizer. For direct methanol fuel cells, the fuel is liquid methanol. In accordance with the general principles of the invention, the composite electrolyte comprises: (i) an inorganic cation exchange material, (ii) a silica-based material, and (iii) a polymer-based material. The invention allows, however, any combination of these materials to be used for producing a proton exchange membrane. The preferred inorganic cation exchange materials include clays, zeolites, hydrous oxides, and inorganic salts, which are described, for example, in Amphlett, C.B., Inorganic Ion Exchangers, Elsevier Publishing Co., Amsterdam, 1964, and Qureshi et al, Inorganic Ion Exchangers in Chemical Analysis, CRC Press, Boca Raton, 2000. Preferred zeolites include heulandite, analcite, chabazite, phillipsite, ZK5, ZK4, mordenite, and the linde family. Preferred hydrous oxides include ferrous hydroxide, magnesium hydroxide, aluminum hydroxide, and beryllium oxide. Preferred inorganic salts include zirconium phosphate, titanium phosphate, zirconium arsenate, tin phosphate, and cerium phosphate. Preferred clays include aluminosilicate-based exchange materials selected from the group consisting of montmorillonite, kaolinite, vermiculite, smectite, hectorite, mica, bentonite, nontronite, beidellite, volkonskoite, saponite, magadite, kenyaite, zeolite, alumina, rutile, and mixtures thereof. These clays are commercially available. For example, montmorillonite is available from Aldrich Fine Chemicals. . The clays can be tailored to make them more compatible with organic matrices. Modifications include, but are not limited to exfoliation which helps to separate the platelets of inorganic substance more effectively. Typically, the composite electrolyte is comprised of about 0.1% to about 99% inorganic cation exchange material, and preferably about 0.1 % to about 30% (all percentages herein are based on weight unless otherwise noted). The inorganic cation exchange materials serve a number of functions. Foremost, these materials help increase ion exchange capacity (IEC). Figure 2 shows the IEC values for several membranes with different amounts of montmorillonite (MMT) and also with modified montmorillonite (mMMT). Montmorillonite is just one of the clay materials that may be used solely or in combination with other additives. The modified montmorillonite (Nanomer 1.24 TL, by Nanocor, Inc., Arlington Heights, IL) consists of montmorillonite treated with aminododecanoic acid. Other possible modifiers of inorganics include trimethyl stearate ammonium (Nanomer, 1.28E, by Nanocor, Inc., Arlington Heights, IL), Octadecylamine (Nanomer, 1.30 E, by Nanocor, Inc., Arlington Heights, IL), methyl dihydroxy hydrogenated tallow ammonium (Nanomer, 1.34 TCN, Nanocor, Inc., Arlington Heights, IL), etc. The layered structure of montmorillonite is created by strong electrostatic forces that hold the adjacent clay platelets together. The aspect ratios of the stacked platelet structure are far greater than that of the individual platelets which are on the order of 100-1500 nm. Nano-sized platets may increase the modulus of the matrix without a concomitant decrease in ductility; as is generally observed when micron-sized additives are used. Therefore, the benefit of using high aspect ratio platelets can be realized only if the stacks are separated, in order to evaluate the effect of additives on the IEC, the base proton conducting polymer is identical in all the cases. One can see from Figure 2 that as the percentage of montmorillonite is increased, IEC increases and a maximum is observed when the modified montmorillonite amount is about 3 wt.%. In comparison, the effects of montmorillonite on IEC values are better in the case of modified montmorillonite. Other attributes are affected by the introduction of additives to the composition of the polymer, including proton conductivity. Figure 3 illustrates the empirical results of proton conductivity at a particular temperature of 90 °C for various compositions of composite polymer electrolyte membranes. The two probe conductivity method for analyzing the proton conductivity of these same membranes is similar to a method described by Mueller and Urban. See Mueller et al. "Characterization of direct methanol fuel cells by an impedance spectroscopy", Journal of Power Sources, 75, (1998), 139-143. Irrespective of the membrane composition, as temperature is increased, proton conductivity increases. However, the proton conductivities of the membrane formulations with a higher amount of inorganic cation exchange materials have higher conductivities at elevated temperatures. Higher conductivities at elevated temperatures are useful as it increases reaction kinetics, reduces catalyst poisoning, increases overall efficiency, and can help reduce the cost of the overall fuel cell system. Figure Evidently, as one would expect based on the IEC values, the maximum proton conductivity value is observed in Figure 3 for the composite polymer electrolyte membrane with 3 wt.% modified montmorillonite additive. As can be further observed in Figure 4, the addition of the inorganic material significantly reduces water swelling. In addition to reducing the water swelling of the membrane, the incorporation in the polymer of some of the inorganic materials as those disclosed here also improves the water retention capability of the membrane at elevated temperatures. This is critical to achieving adequate conductivities at elevated temperatures. What is significant is that the addition of montmorillonite helps the membrane to retain water at elevated temperatures with very low heating ramp. Due to its high conductivity at elevated temperatures and moisture retaining capabilities, the composite electrolyte membrane is expected to support fuel cell operations up to 120° C. Lastly, the addition of inorganic materials such as clays in the polymer matrix tends to increase the mechanical strength of the membrane. The inorganic cation exchange materials disclosed in the present invention also tend to improve the structural integrity of the membrane, in particular, by reducing the degree of dimensional fluctuations caused by electrochemical cell temperature variations and/or variations in composite electrolyte membrane water content. In some cases tensile strength more than doubles with the addition of inorganic cation exchange materials in either dry or wet conditions. For example, Figure 5 highlights the effect of inorganic cation exchange materials on tensile strength in both wet and dry conditions. By adding 3 wt. % modified montmorillonite to the polymer matrix the dry modulus increases by approximately 10%. Moreover, the Young's modulus (Figure 6) of the composite polymer electrolyte membrane is increased by about 20 %. In general, composite polymer membranes with unmodified montmorillonite show much higher tensile strength and young's modulus as compared to the pristine polymer membranes (membranes without additives). However, the composite membranes using modified montmorillonite as an additive show even better mechanical behavior compared to the pristine and composite membranes with montmorillonite. This can be explained by the better exfoliation of the montmorillonite clay particles with high aspect ratios. When used in the polymer matrix of a membrane structure, the silica-based material has many positive affects. These include increasing the IEC, increasing proton conductivity, reducing the swelling of hydrophilic materials, and increasing the mechanical strength. Silica based materials increase the ion exchange capacity of the composuite membrane, especially when inorganic cation exchange materials are present. The silica-based material is comprised of materials containing silica, silicates, and/or silicates having organic groups such as silicate esters or any combinations thereof. Preferred silica-based materials include a colloidal silica comprising discrete spheres of silica that is available under the trade name LUDOX Aldrich Fine Chemicals. Another preferred silica- based material is a silica based binder known by tetraethylorthosilicate (TEOS) also from Aldrich Fine Chemicals. Typically, the composite electrolyte contains about 0.1% to about 70% and preferably from about 0.1% to about 30% of the silica-based material. In some cases, the addition of a silica-based material to kaolinite increases kaolinite 's cation exchange capacity by 200% . However, regardless of mechanisms, the proton conductivity of the composite electrolyte membrane containing TEOS and kaolinite in the base polymer is greater than a membrane containing just kaolinite. Indeed, as shown in Figure 7, the proton conductivity of the composite electrolyte membrane containing TEOS and Clay (montmorillonite) in the polymer matrix is greater than a membrane containing just montmorillonite or TEOS, indicating that materials such as TEOS help improve membrane conductivity. In the composite electrolyte, the polymer-based material is comprised of a polymer, or polymers that serve as the adhesive or base for the other components of the composite electrolyte. Any suitable polymer that is sufficiently chemically inert, mechanically durable, and ductile to withstand the operation conditions of electrochemical devices, particularly those of PEM fuel cells, can be employed. The general polymer structure may be linear, branched, or a network or a combination thereof. It may contain aryl structures as well as inorganic moieties. Preferred polymer materials include acrylonitrile/butadiene/stryene rubber (ABS), styrene butadiene/acrylate/acetate polymer blends, epoxides, and thermoplastics, or mixtures thereof. Preferred thermoplastics include, but are not limited to, polypropylene, polycarbonate, polystyrene, polyethylene, polyaryl ether sulfones, poly aryl ether ketone, and polysulfones. Particularly, preferred polymers have functional groups such as, sulfonate, phosphate, carbonate, amide, or imide groups, which have inherent proton conducting capabilities. Thus, the polymer- based material, besides increasing the mechanical strength of the composite electrolyte membrane, also increases the proton conductivity during electrochemical cell operation. Typically, the composite electrolyte is comprised of about 0.1% to about 99.9% and preferably from about 40% to about 99.9% polymer-based material. The composite electrolyte does not require perfluoronated polymers such as Nafion® or its derivatives. The composite electrolyte can further include additives such as preservatives, thixotropy and viscosity control agents, crosslinking agents, conditioners, plasticizers, water control agents, proton conducting materials and other enhancing components commonly known in the art. However, the dried composite electrolyte membrane consists essentially of three primary components, namely: (i) an inorganic cation exchange material, (ii) a silica- based material, and (iii) _.a polymer-based material. Indeed, in preferred embodiments, the three primary components make up at least 90% of the solids of the composite electrolyte. Figure 8 highlights the performance of an exemplary fuel cell with a particular composite membrane embodiment. It can be observed that the composite membrane with montmorillonite in accordance with the present invention performs better than Naifon^® (current density and power density) under identical operating conditions. It is noted that although this example compares the cell output performance for the two types of membranes, i.e., the particular embodiment of composite electrolyte and Nafion^®, i t does not represent the best performance that can be achieved by fuel cells embodying composite electrolytes in according with the present. Overall, the composite electrolyte preferably has a proton conductivity on the order of 0.005 S/cm and more preferably of at least 0.05 S/cm below 100°C. This will enable the rapid proton transfer from anode to cathode when the composite electrolyte is used as a proton exchange membrane in a fuel cell. As compared with conventional membranes, the various attributes of a composite electrolyte in accordance with the present invention provide for better manufacturing results. For example, the composite membrane tends to be more physically robust to adequately withstand MEA manufacturing processes and pressure differentials within a fuel cell stack. Furthermore, the membrane tends to have a higher water retaining potential. This will enable higher temperature operation without sacrificing proton conductivity. Finally, the membrane tends to be more chemically robust so as not to degrade in the stack environment. In manufacturing, the composite membranes of the present invention can be fabricated by thoroughly mixing the membrane components in a solvent to minimize agglomeration. Water can be used as the solvent; raising the pH of the water on occasion helps to stabilize the particles in the slurry and facilitate mixing. Furthermore, other solvents such as, but not limited to, n-methyl pyrrilidione, dimethyl sulfone, dimehyl acidimide, and dimethyl formaldehyde may be used. The viscous solution is poured over a substrate and leveled to a uniform thickness. After evaporation of the solvent and removal from the substrate, the membrane is cut to size and is ready for use. Heat, or reducing the pressure can be applied to facilitate evaporation. A preferred technique is a tape casting method whereby the slurry of components is poured onto a silicon coated polyester (MYLAR) sheet. A doctor blade moving across the slurry adjusts the height to the desired thickness ranging from about 0.5 μm to about 500 μm and preferably from about 100 μm to about 300 μm. Evaporation of the solvent takes place in a controlled temperature and humidity environment. Other methods of membrane assembly include extrusion and tray casting.

EXAMPLES The following describes composite membrane formulations and testing as a proton exchange membrane. The description, although not exhaustive, serves to familiarize the reader with composite membrane production methods in accordance with the principles of the present invention. Before testing, as part of a production method, the formulation involves adding a Montmorillonite or modified montmorillonite (1.24 TL, Nanomer, IL, USA) to different samples of sulfonated polyether ether ketone (SPEEK) to create membranes with 0, 3, 5, 7, 10 and 15 wt % loading of clay. SPEEK and clay mixtures are grounded to disperse the clay uniformly and aid in dissolution. Following grinding, the mixture of SPEEK and clay are dissolved in approximately 10 ml distilled N,N-dimethyl formaldehyde (DMF) by stirring for about 2 hours using a magnetic stir bar. Subsequently, the solution of DMF containing dissolved SPEEK and clay are sonicated for about 4 minutes using an Ultrasonic Homogenizer. The sonicated solution is stirred and heated to allow the solvent (DMF) to evaporate. Heating and stirring continue until the solution thickens and attains a casting consistency. The polymer and/or composite polymer solution may be prepared by using any of the solvents not limited to N,N-dimethyl formaldehyde, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide alcohols such as isopropyl alcohol, and t-butyl alcohol. Next, the solution is degassed in a vacuum oven. After vacuum treatment, the resulting solution is poured out onto a clean glass plate and cast into approximately 50 μm thick films using a doctor blade. The curing protocol proceeds as follows: first, the cast film is annealed in a convection oven for about 12 hours at about 70 °C; next, the cast film is placed in a vacuum oven for about 12 hours at about 100°C; after which it is subjected to vacuum for approximately 12 hours in an oven which is maintained at about 130°C. Then, the cured films are peeled off the glass plate using a blade and protonated. The films are stored in ultra-pure water until ready for use. In testing, proton exchange membranes produced by the foregoing method showed improved mechanical properties, water uptake, and conductivity over unmodified SPEEK of the same sulfonation level. Furthermore, these membranes displayed higher conductivities and lower methanol crossover values than those of Nafion®, making them well suited for use as proton exchange membranes in hydrogen oxygen fuel cells and DM fuel cells. In sum, the discovery of composite polymer membranes and of the process of producing such membranes promotes the use of fuel cells as a viable alternative to existing energy sources. Composite polymer electrolyte membranes, particularly those with additives such as montmorillonite, exhibit better physiochemical properties and thus provide superior fuel cell performance.

Claims

What is claimed is:

1. A composite electrolyte for use in electrochemical fuel cells, comprising: (i) an inorganic cation exchange material; (ii) a silica-based material; and (iii) a proton conducting polymer-based material, wherein the inorganic cation exchange material comprises about 0.1 wt% to about 99 wt% of the composite electrolyte.

2. The composite electrolyte of claim 1, wherein the silica-based material comprises about 0.1 wt% to about 70 wt%, and the proton conducting polymer-based material comprises about 0.1 wt% to 99.9 wt% of the composite electrolyte.

3 The composite electrolyte of claim 1 wherein the inorganic cation exchange material is selected from the group consisting of clay, zeolite, hydrous oxide, and inorganic salt.

4. The composite electrolyte of claim 3, wherein the clay includes an aluminosilicate-based exchange material selected from the group consisting of montmorillonite, kaolinite, vermiculite, smectite, hectorite, mica, bentonite, nontronite, beidellite, volkonskoite, saponite, magadite, kenyaite, zeolite, alumina, rutile.

5. The composite material of claim 3, wherein the clay is modified to make it more compatible with organic matrices, a clay modification including exfoliation which helps to separate platelets of inorganic substance.

6. The composite electrolyte of claim 3, wherein the clay includes a modified montmorillonite consisting of montmorillonite treated with a modifier material selected from a group consisting of aminododecanoic acid, trimethyl stearate ammonium, octadecylamine, and methyl dihydroxy hydrogenated tallow ammonium.

7. The composite electrolyte of claim 1 wherein the inorganic cation exchange material comprises about 0.1 wt% to about 30 wt%, the silica-based material comprises about 0.1 wt% to about 30 wt%, and the proton conducting polymer-based material comprises about 40 wt% to 99.9 wt% of the composite electrolyte.

8. The composite electrolyte of claim 1 wherein the proton conducting polymer-based material has a linear, branched, or network morphology.

9. The composite electrolyte of claim 1 wherein the proton conducting polymer-based material includes material selected from the group consisting of aciylonitrile/butadiene/stryene rubber (ABS), styrene butadiene/acrylate/acetate polymer blends, epoxides, and a thermoplastic material.

10. The composite electrolyte of claim 9 wherein the thermoplatic material is selected from a group consisting polypropylene, polycarbonate, polystyrene, polyethylene, polyaryl ethers sulfones, poly aryl ether ketone, and polysulfones.

11. The composite electrolyte of claim 1 wherein the proton conducting polymer-based material has a functional group element selected from a group consisting of sulfonate, phosphate, carbonate, amide, and imide, wherein each such functional group element has proton conducting capabilities.

12. The composite electrolyte of claim 1, further comprising an additive selected from a group consisting of preservative, thixotropy and viscosity control agent, crosslinking agent, conditioner, plasticizer, water control agent, and proton conducting material.

13. The composite electrolyte of claim 1 wherein the inorganic cation exchange material, the silica-based material and the proton conducting polymer-based material comprise 90 wt % or more of the solids content of the composite electrolyte.

14. The composite electrolyte of claim 1 wherein the composite electrolyte when measured in the substantially dried state consists essentially of the inorganic cation exchange material, the silica-based material and the proton conducting polymer-based material.

15. The composite electrolyte of claim 1 wherein the composite electrolyte has a proton conductivity of about 0.05 S/cm or higher

16. The composite electrolyte of claim 1 wherein the silica-based material includes materials containing one or more of silica, silicate , and silicate having an organic element.

17. The composite electrolyte of claim 1 wherein the silica-based material is either colloidal silica containing discrete spheres of silica or tetraethylorthosilicate.

18. An electrochemical fuel cell, comprising: (i) an anode; (ii) a cathode; (iii) a fuel supply to the anode; (iv) an oxidant supply to the cathode; and (v) a composite electrolyte positioned between the anode and cathode and including (a) an inorganic cation material, (b) a silica-based binder, and (c) a polymer-based binder, wherein the inorganic cation exchange material comprises about 0.1 wt% to about 99 wt%, of the composite electrolyte.

19. The electrochemical fuel cell of claim 18 wherein the silica-based material comprises about 0.1 wt% to about 70 wt%, and the proton conducting polymer-based material comprises about 0.1 wt% to 99.9 wt% of the composite electrolyte.

20. The electrochemical fuel cell of claim 18 wherein the inorganic cation exchange material comprises about 0.1 wt% to about 30 wt%, the silica-based material comprises about 0.1 wt% to about 30 wt%, and the proton conducting polymer-based material comprises about 40 wt% to 99.9 wt% of the composite electrolyte.

21. The electrochemical fuel cell of claim 18 wherein the inorganic cation exchange material is selected from the group consisting of clay, zeolite, hydrous oxide, and inorganic salt.

22. The electrochemical fuel cell of claim 21 wherein the clay includes an aluminosilicate- based exchange material selected from the group consisting of montmorillonite, kaolinite, vermiculite, smectite, hectorite, mica, bentonite, nontronite, beidellite, volkonskoite, saponite, magadite, kenyaite, zeolite, alumina,and rutile.

23. The electrochemical fuel cell of claim 21 , wherein the clay is modified to make it more compatible with organic matrices, a clay modification including exfoliation which helps to separate platelets of inorganic substance.

24. The electrochemical fuel cell of claim 21, wherein the clay includes a modified montmorillonite consisting of montmorillonite treated with a modifier material selected from a group consisting of aminododecanoic acid, trimethyl stearate ammonium, octadecylamine, and methyl dihydroxy hydrogenated tallow ammonium.

25. Theelectrochemical fuel cell ofclaim 18 wherein the polymer-based material has linear, branched, or network morphology.

26. The electrochemical fuel cell ofclaim 18 wherein the polymer-based material includes material selected from the group consisting of acrylonitrile/butadiene/stryene rubber (ABS), styrene butadiene/acrylate/acetate polymer blends, epoxides, polypropylene, polycarbonate, polystyrene, polyethylene, polyaryl ethers, and polysulfones.

27. The electrochemical fuel cell of claim 18 wherein the inorganic cation exchange material, the silica-based material and the polymer-based material comprise 90 wt % or more of the solids content of the composite electrolyte.

28. The electrochemical fuel cell of claim 18 wherein the composite electrolyte when measured in the substantially dried state consists essentially of the inorganic cation exchange material, the silica-based material and the polymer-based material.

29. The electrochemical fuel cell ofclaim 18 wherein the composite electrolyte has a proton conductivity of about 0.05 S/cm or higher.

30. A method of fabricating a composite electrolyte for use in an electrochemical fuel cell, comprising: (i) applying onto a surface of a substrate a viscous liquid composition of (a) an inorganic cation exchange material, (b) silica-based material, (c) a polymer-based material, and (d) a solvent-dispersant; (ii) spreading the viscous liquid composition to form a uniform thickness layer on the substrate; and (iii) allowing the solvent to evaporate from the viscous liquid composition to yield the composite electrolyte, wherein the inorganic cation exchange material comprises about 0.1 wt% to about 99 wt% of the composite electrolyte.

31. The method of claim 30, whereinthe silica-based material comprises about 0.1 wt% to about 70 wt%, and the polymer-based material comprises about 0.1 wt% to 99.9 wt% of the composite electrolyte.

32. The method ofclaim 30 wherein step (ii) includes drawing the viscous liquid composition through a doctor blade assembly.

33. The method ofclaim 30 wherein step (iii) includes heating the viscous liquid composition.

34. The method ofclaim 30 wherein the inorganic cation exchange material comprises about 0.1 wt% to about 30 wt%, the silica-based material comprises about 0.1 wt% to about 15 wt%, and the polymer-based material comprises about 40 wt% to 99 wt% of the composite electrolyte.

35. The method ofclaim 19 wherein the inorganic cation exchange material is selected from the group consisting of clay, zeolite, hydrous oxide, inorganic and salt.

36. The method ofclaim 35 wherein the clay includes an aluminosilicate-based exchange material selected from the group consisting of montmorillonite, kaolinite, vermiculite, smectite, hectorite, mica, bentonite, nontronite, beidellite, volkonskoite, saponite, magadite, kenyaite, zeolite, alumina, and rutile.

37. The method ofclaim 35, wherein the clay is modified to make it more compatible with organic matrices, a clay modification including exfoliation which helps to separate platelets of inorganic substance.

38. The method ofclaim 35, wherein the clay includes a modified montmorillonite consisting of montmorillonite treated with a modifier material selected from a group consisting of aminododecanoic acid, trimethyl stearate ammonium, octadecylamine, and methyl dihydroxy hydrogenated tallow ammonium.

39. The method of claim30 wherein the polymer-based material has a linear, branched, or netted morphology.

40. The method ofclaim 30 wherein the polymer-based material includes one of acrylonitrile/butadiene/stryene rubber (ABS), styrene butadiene/acrylate/acetate polymer blends, epoxides, polypropylene, polycarbonate, polystyrene, polyethylene, polyaryl ethers, and polysulfones.

41. The method of claim 30 wherein the solvent-dispersant comprises water, n-methyl pyrrilidione, dimethyl sulfone, dimethyl acidimide, dimethyl, and formaldehyde.

42. The method ofclaim 30 wherein the inorganic cation exchange material, the silica-based material and the polymer-based material comprise 90 wt % or more of the solids content of the composite electrolyte.

43. The method of claim 30 wherein the composite electrolyte when measured in the substantially dried state consists essentially of the inorganic cation exchange material, the silica- based material and the polymer-based material.

44. The method of claim 19 wherein the composite electrolyte has a proton conductivity of about 0.05 S/cm or higher.

45. A method for producing a composite membrane, comprising:

(i) grinding a sulfonated polyether ether kethon (SPEEK) and clay mixture and dissolving the mixture in a distilled dimethyl formaldehyde (DMF) to form a solution; (ii) heating the solution until it thickens and attains a casting consistency;

(iii) degassing the solution in a vacuum oven;

(iv) casting the solution into a film on a glass surface using a doctor blade;

(v) curing the film; and

(vi) peeling the film from the glass.

46. The method ofclaim 45, wherein the dissolving in step (i) ) is performed by stirring for about 2 hours using a magnetic stir bar.

47. The method of claim 45, wherein the solution is stirred while heated, and wherein the DMF evaporates.

48. The method ofclaim 45, wherein the film is about 50 μm thick.

49. The method of claim 45, wherein the curing includes, (a) annealing the film in a convection oven, and (b) maintaining the film in a vacuum for a predetermined time period at a predetermined temperature.

50. The method of claim 45, further comprising: storing the film in ultra-pure water until it is ready for use.