CZ2003346A3 - Hydrogen permeable membrane for use in fuel cells, and partial reformate fuel cell system having reforming catalysts in the anode fuel cell compartment - Google Patents

Abstract

The electronically insulating proton conductor (C) is bonded or applied as film on protons permeable material (D) with a dense phase, in such a thickness that the C / D combination has proton conductivity at a preferred medium temperature range 175-550 ° C. The C / D combination is integrated into the system high temperature membrane electrode (MEA) an electrolyte that is incorporated into the fuel cell; can operate in this medium temperature range. Fuel the cell, on the other hand, is incorporated into the fuel system a cell that has a fuel reformer in the flow field of the mixture fuel entering the fuel cell or system, u which fuels the fuel cell from an external fuel cell reformer.

Description

Hydrogen-permeable membrane for use in fuel cells and a partial reformate fuel cell assembly having reforming catalysts in the anode space of the fuel cell

Related Applications

Priority Application No. 60/222 128 filed July 31, 2000 for the title: Partial Fuel Cell Reformate and Provisional Application No. 60/244 208 filed on October 31, 2000 for the title A Proton Exchange Membrane, A Partial applies to this application. Fuel Cell Reformate, And A Partial Fuel Cell Reformate With A Reformer In The Flow Field, which are hereby incorporated by reference.

Technical field

The present invention relates to a composite electrolyte system for use either as a separate medium temperature fuel cell or in fuel cell systems with methanol reforming catalysts within the anode space. The composite electrolytic system comprises a carrier film or metal hydride mesh which is supported by electronically insulated proton conductors on one or both sides of the carrier film.

BACKGROUND OF THE INVENTION

Fuel cells are electrochemical devices that convert the chemical energy of a reaction directly into electrical energy. Chemical energy is the difference between the starting chemicals and the energy of the chemicals produced. The reaction is a process in which chemicals are converted from the starting chemicals to the chemicals of the product while maintaining the same total mass. In fuel cells, the anode reaction is an oxidation reaction and the cathode reaction is a reduction reaction. The oxidation reaction involves loss of electrons, while electron recovery is a reduction reaction. The fuel cell is a galvanic cell. The galvanic cell is a device for extracting energy from the reaction as electrical work. Maximum electrical work is equivalent to the conversion into free energy that occurs during the reaction.

For example, the standard free energy reaction

2H ₂ (gas) + 0 ₂ (gas) -> 2H ₂ O (liquid) is a change in free energy when two moles of pure hydrogen at 1 bar react with 1 mole of pure oxygen gas at 1 bar to produce liquid water of of the same pressure. The standard free energy change for this reaction is -474.26 kilojoules. This is how much energy is available for non-expansion work that involves electrical work. The liquid is a condensed phase. The change in free energy for a fuel cell reaction, such as the formation of water from hydrogen and oxygen, is related to the cell's potential according to the following reaction:

ÁG = nFE where n is the amount of electrons (in moles) transferred between the electrodes when a stoichiometric reaction occurs. F is the Faraday constant of 96500 coulombs per mole and E is the cell voltage. The electrical work that is performed when the charge paths from the anode to the cathode is equal to the product of the cell voltage and the drive current multiplied by the withdrawn current.

A battery is a power storage device. The maximum energy available is given by the amount of chemical reactant stored in the battery itself. The battery stops producing electricity when the chemical reactants are consumed (ie emptied). In the secondary battery, recharging regenerates the reactants, thereby supplying energy to the battery from an external

Β «

• ♦ BB ΒΒΒΒΒΒΒ * Β Β zdroje zdroje zdroje zdroje zdroje zdroje zdroje zdroje zdroje zdroje. The fuel cell, on the other hand, is an energy conversion device that theoretically has the ability to generate electricity for as long as the fuel and oxidizing agent are fed to the electrodes. In fact, degradation, primary corrosion, component malfunction limits the practical operating life of the fuel cells.

Fuel cells have been generating energy for space travel (shuttles) for decades. However, the fuel used in the shuttle fuel cells is pure, liquid hydrogen.

In conventional fuel cells, the electrolyte is catalyzed on both faces of a two-dimensional membrane. One face is the anode side where the fuel is oxidized and the opposite face is the cathode side where the oxygen is reduced. For polymer electrolyte fuel cells, this three-layer system is commonly referred to as a membrane electrode system (MEA). The three layers is a polymer electrolyte sandwiched between two catalyst layers.

Gasoline, diesel, methane, and alcohols do not have adequate electrochemical activity to be used directly with the prior art polymer electrolyte (PEFC) fuel cells for high energy applications. There is a need to use a catalytic-chemical fuel processor to convert these fuels into hydrogen-rich fuel gases. The fuel processor for automotive fuel cell engines must be able to start very quickly, then quickly draw energy and operate efficiently over a wide range of conversion speeds. Fuel conversion also needs to be substantially perfect over the entire load range. The level of carbon monoxide in the treated fuel entering the shaft must be very low to prevent poisoning of the anode catalysts.

* 0 · 0 0 0 0 0 0

0 000 00 0 0000 000 0 0 * 0 00 0 0000 00 00 · 0000

The chemical reactions that affect the fuel processor design for the two alternative reactions used in the first methanol conversion step, i. H ₃ COH or gasoline {e.g. H ₃ C (CH ₂ ) _and CH ₃ ) are listed below:

Steam generation (1) 2 H ₃ COH + H ₂ 0 (steam) + heat -> 5 H ₂ + CO + CO ₂ (2) H ₃ C (CH ₂ ) ₆ CH ₃ + 12 H ₂ O (para) + heat -> 21 H ₂ + 4 CO + 4 CO ₂

Partial oxidation (3) 2 H ₃ COH + 0 ₂ (air) -> 3 H ₂ + CO + CO ₂ H ₂ 0 + heat (2) H ₃ C (CH ₂ ) ₆ CH ₃ + 71 0 ₂ (air) -4 e H ₂ + 4 CO + 4 CO ₂ + 3 H ₂ 0 + heat

The steam reforming reactions described in the above equations need a catalyst. Catalysts are included in the catalytic-chemical-fuel processor. For the purposes of this patent application, a reforming catalyst is any catalyst that increases the rate of hydrogen formation. This will include water gas conversion catalysts that convert CO and water to hydrogen and CO ₂ . Reaction (1) can be considered as a combination of methanol cracking and water gas conversion. Reaction (1) can be decomposed into (1A) and (IB).

(IA) 2H ₃ COH -> 2 CO + 4 H ₂ (IB) 2 CO + 2H ₂ 0 -> 2 CO + 2H ₂

However, in systems in practice, the second reaction is not completed. That is why the reform fuel is not contaminated with CO. Both (IA) and (IB) require catalysts. (IA) is the cracking reaction of methanol, while (IB) is the water gas conversion reaction. Therefore, for conversion • ♦ · Β · · · · · · · · · · · · · · «« «« «« «

II to vodík které Β · reakci Β Β methanol to hydrogen, catalysts that activate the cracking reaction, water gas conversion catalysts, or dual function catalysts that allow both reactions, all referred to as reforming catalysts. These catalysts may be incorporated into a separate reactor outside the fuel cell or may be incorporated into the fuel cell itself. When the catalyst is incorporated into the fuel cell, this is referred to as internal reforming. A reactor or set of reactors that chemically convert fuel to hydrogen is also called a Syngas reactor generator. By-products are always produced, including CO ₂ and CO. Other by-products may also be manufactured.

The H ₂ content in the reformed methanol or gasoline is about 0.189 kg or 0.430 kg H ₂ / kg fuel. The reform process gives H ₂ diluted CO ₂ and low CO levels. Within the operating temperature (T) range of the polymer electrolyte fuel cells, the water gas reformate (WGS) and the preferred oxidation (PROX) reactor contain CO at the pph level, which is sufficient to stop the Pt alloy catalyst. The WGS yield contains about 1% CO, which is still sufficient to stop the anode. The PROX unit is used to further reduce the CO content to a tolerance limit of about 10 ppm of a typical anode catalyst (PtRu). The development of CO-tolerant anodes eliminates the need for PROX and WGS units. Today, there are no anode catalysts that could withstand a 1% CO content of the WGS reactor output at the operating temperature of the polymer electrolyte fuel cell. The most commonly used anode catalyst is carbon on a PtRu support. Alternatives such as PtMo have also been explored, but the stability issue with PtMo requires research. Therefore, the search for a better catalyst should be extended to research on High Temperature Electrolytic Systems (HTE). Phosphoric acid fuel cells (PAFCs) do not require a PROX unit because they operate at 20 ° C. Although CO is not a fuel

4 4 9 9 9 4

9 99 99 φ * _V 49 49 * 4 4 4 · 4 · 4 9 9 • 9 9 9 9 9 9 49 49 at 200 ° C, it is not poison. However, PACF suffers from corrosion problems associated with phosphoric acid electrolyte.

There are other reasons for increasing the FC working temperature even when using H ₂ . At high efficiencies (high voltage cells), the polarization at the anode could be less than 30 mV, judging the cell voltage of hundreds of mV from the thermodynamic value due to cathode polarization (or cathode losses). The reduction kinetics of the four electron oxygen would be substantially improved if high temperature electrolytic systems were developed. Therefore, there are two key reasons for the development of high temperature electrolytic systems (1) to reduce CO poisoning and (2) to improve the O ₂ reduction kinetics. High temperatures of the electrolyte systems would significantly reduce the volume of the fuel processor / FC system (the PROX unit could be drained and the size of the water gas reformer could be reduced or possibly eliminated). Successful development of high temperature electrolytes could provide a relaxation of the fuel reformer performance requirements. The use of such membrane electrolyte systems (MEA) even at higher temperatures would have an extraordinary effect on the design of compact systems for portable, transport and stationary energy.

Solid state proton conductors are candidates for sensors, batteries, fuel cells, electrolysers, etc. A brief overview of the solid state types and principles of proton conductors and temperature dependencies of these conductors is given in Norby's publication: Solidstate Protective Conductors: Principles, Properties, Progress and Prospects Solid State Ionics, 125, pp. 1-11 (1999), which are incorporated herein by reference. Norby states in the annotation that it is very necessary to develop electrodes for high- and medium-temperature proton conductors. The above-mentioned edition of Solid State Ionics is from the 9th International Conference on solid state proton conductors.

4 4 * 444 4 4

4 44

The meeting contains over 50 articles on solid state proton conductors.

The prior art polymer electrolyte fuel cells typically use conductive polymers as an electrolyte membrane in MEA. Known proton-guiding polymers are low temperature conductors operating below 100 ° C. On the other hand, medium and high temperature proton conductors operate in temperature ranges of 1000 to 650 ° C and 650 ° C or more.

MEA is the core of the fuel cell. Proton-guiding polymers are used as electrolyte in PEFPC. Nafion ™ is an example of a proton-guiding polymer. Although electrolytes for fuel cells are necessarily proton conductors, they do not conduct electrons {i. are electron insulators). This Nafion is an example of an electronically insulated proton conductor. EIPC is a material that conducts protons or hydrogen but does not conduct electrons. PEFCs usually operate at temperatures below 100 ° C. The upper limit is given by the properties of the polymer electrolyte (usually perfluorinated sulfonated polymers such as Nafion ™) which dehydrates at a temperature above 100 ° C. Maintaining water (water management) in the polymer is necessary for high conductivity of protons. When the temperature rises above the boiling point of water, the polymer membrane dehydrates. Dehydration of the membrane reduces conductivity.

With known PEFCs, the conductivity decreases as the temperature increases. In particular, the proton conductivity of Nafion ™ decreases as the temperature increases. Typically, the thickness of Nafion used in fuel cells is between 0.0508 mm to 0.1778 mm (2 to 7 miles, where miles is a thousandth of an inch, ie, 0.0254 mm). Such thick layers are free-standing films. It is possible to maintain the hydration of the membrane by increasing the pressure. Increasing pressure is a way of affecting water management because «•« 9 9 9 9 · 99 * * 9 999 * 9 9 9999 9 9 9 9

9 9 9 9 9999

99 99 9 99 «φ The boiling point of water increases with increasing pressure. However, operating the fuel cell at higher pressure requires the use of parasitic energy to operate the compressors. Maintaining a higher pressure would reduce the energy density of the fuel cell system.

The attached Fig. 1 is Fig. 1 from Norby. It shows selected data for proton conductivity as a function of the inverted temperature value. Norby states that many classes of proton conductors are members that have a proton conductivity of up to 10 ^-3 to 10 ^-2 S / cm at a certain temperature. The proton conductivity shown in Figure 1 for Nafion and HCL and H ₃ PO ₄ solutions are in the ranges in which these materials are useful as proton conductors.

Proton conductors containing Nafion, HCl and H ₃ PO ₄ have several disadvantages. Nafion requires water. Phosphoric acid fuel cells have a matrix such as alloyed polybenzimidazole soaked with phosphoric acid. The working temperature of these acids is also limited by their volatility. Also, the anion (or conjugate base) of phosphoric acid (i.e., phosphate) poisones the platinum cathode catalyst.

Norby states that at higher temperatures the protonic conductivity decreases due to (1) reversible or irreversible loss of vehicle water (eg, in proton-conducting polymers), (2) due to decomposition or melting of hydrates, hydroxides or acid salts, or (3) ) due to reversible loss of protons (water) from oxides. Therefore, proton conductivities are usually functional over relatively narrow temperature ranges.

The conductivity units are S / cm. where S is Siemens. Siemens is the inverse of Ohm (ie 1 / Ω). Referring to Fig. 1, Norby concludes that at present, solid proton conductors are not »9 9 • 9 99 # 9 9 9 · 99 · · * * 9 * 9 · 9 · 9 9 · 9 9 9 9 · 9 9 9 · atelné · · atelné atelné · · atelné atelné · atelné s s · However, proton conductors essentially operate at substantially lower temperatures and can offer the highest conductivity at medium and low temperatures. However, there are no proton conductors operating satisfactorily in the gap between about 200-500 ° C, as shown in Fig. 11, when the gap may seem small in the Arhnian diagram, it overlaps the most important and most desirable operating temperature range for both chemical processes and conversion processes. Narrowing this gap is of primary concern in developing proton conductors for practical use.

Therefore, there is a need for a system having a proton conductivity in the region of the gap of Fig. 1. In particular, it is necessary to find an electronically insulating proton conductor containing no liquid phase, such as water in Nafion or H ₃ PO ₄ the gaps of FIG. 2.

SUMMARY OF THE INVENTION

An embodiment of the present invention is an electron insulating proton conductor having a conductivity within the gap of Fig. 1.

Another embodiment is an electron insulating proton conductor having a proton conductivity in the gap of Fig. 2, wherein the electron insulating proton conductor contains no liquid phase.

Further embodiments relate to a proton conductive membrane comprising an electronically insulated proton conductor having a proton conductivity within the gap of Fig. 1 or comprising a proton conductive membrane having a proton conductivity within the gap of Fig. 2, wherein:

Φ Φ · * · · · · ·

the electronically insulated proton conductor contains no liquid phase.

An embodiment of the present invention is a fuel cell comprising a proton conductive membrane, comprising an electronically insulated proton conductor having a proton conductivity within the gap of Figure 1 or having a proton conductivity within the gap of Figure 2, wherein the electronically insulating proton conductor contains no liquid phase.

Another embodiment is a fuel cell system comprising a fuel reformer and a fuel cell comprising a proton conductive membrane having a proton conductivity within the gap of Fig. 2, wherein the electronically insulated proton conductor comprises no liquid phase.

Other advantages of the invention will be apparent to those skilled in the art from the following detailed description, where only the best exemplary embodiments of the present invention are described and illustrated. However, it is to be understood that the invention may be practiced as yet other and various embodiments, and the details thereof may be varied from many different aspects without departing from the scope of the invention. Therefore, the drawings and description are to be considered as illustrative only and not restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

An exemplary embodiment of the present invention is illustrated in the accompanying drawings, wherein Fig. 1 shows selected proton conductivity data as a function of the inverse temperature value for some materials;

* * Β β β β β β 0 0 0 0 0 0 0 fig. Fig. 2 shows selected proton conductivity data as a function of inverse temperature for some materials; 3 shows an example of an electrode assembly with a high temperature electrolyte membrane;

Fig. 4 shows a thickness as a function of the inverse temperature of various materials having a proton conductivity equal to the conductivity of Nafion 117 at 80 ° C;

Fig. 5 shows an example of a fuel cell with a membrane electrode assembly;

Fig. 6 shows schematically an embodiment of a medium temperature fuel cell assembly;

Figure 7 shows schematically the reactions taking place in the preparation of silica particles according to one embodiment of the invention; Fig. 8 shows a Pd film with five layers of EIPC on one side, hanging on a frame rack after 20 hours of drying in an NH ₃ atmosphere; Fig. 9 shows changes in ASR (D.cm ³ ) with EIPC thickness in µm (microns);

Fig. 11 shows a fuel cell system with a partial reformate;

Fig. 12 shows the product distribution by internal reforming in an embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term proton conductor means any body capable of producing protons. The body may be a single material or a composite material. A composite material is a set of materials composed of a mixture or combination of two or more macro components differing in the shape and / or composition of the material and which are substantially not soluble in each other.

• 9 • 9 9 9 9 9

999 · 9,999,999 «9 · 9 9 9 9 ·

99 · 9 9 99

For the purposes of this invention. The MEA consists of at least one electrode layer, eg an anode or cathode, wherein the chemical is oxidized or resp. reducing and opposing electrodes, e.g., cathodes or anodes, where the oxidizing agent is reduced or resp. the fuel is oxidized. MEA also has an EIPC that conducts protons but does not conduct electrons. The EIPC of the present invention could be a separate MEA component or incorporated into a transition layer that is electronically insulating yet proton conductive on one face and is a mixed electron-proton conductor on the opposite side. The mixed conductive region serves as a catalytic region and the electron insulating region serves as an electrolyte or EIPC. The catalytic layer is supported on the EIPC side of the transition layer. This would consist of 2 layers of MEA.

This two-layer MEA will typically operate at high temperature such that one side of the MEA proton-conductive composite membrane will not need a catalytic layer because the reaction on the non-catalytic side is calm due to the high temperature. The general concept of MEA is: anode / EIP / C / cathode. The dual-layer MEA will be one in which one of the electrode regions has a gradually changing interface separating the EIPC region from the electrode region. The present invention includes several embodiments of MEA.

In another embodiment of the two-layer MEA, the electrode and counterelectrode are configured as a sandwich and the interface between the electrode and the counterelectrode is an EIPC. An embodiment of the three-layer system will have an EIPC with catalytic electrode and counter electrode layers on both sides of the EIPC. A polymer electrolyte MEA fuel cell using Nafion with catalytic layers on both sides of Nafion is an example of a three-layer MEA.

In another embodiment 5 of the MEA layer, the anode catalyst layer is supported on an EIPC, which in turn is supported on a metal hydride film. The face of the foil facing the anode may have an EIPC layer. 4 4 4 4 4 4 4 4 4 44 44 44 44

44 * 4 * 4 «4 4 deposited on a surface facing the cathode catalyst layer. Another embodiment, a 4-layer MEA, will have an EIPC on only one side of the metal hydride foil.

Typically, the MEA is part of a fuel cell that includes an electrolytic system sandwiched between the anode and cathode catalyst layers. The electrolyte system may comprise a matrix that carries the electrolyte in a liquid phase, a polymer phase, an inorganic phase that conducts oxygen, carbonate, or protons. The electrolyte may be a multi-component system. The anode catalyst could be a high surface area platinum / ruthenium (PtRu) mixed metal catalyst and the cathode can be a large surface area platinum black catalyst. Briefly, an MEA having a PtRu anode, an EIPC, and a Pt cathode is referred to as: PtRu / EIPC / Pt.

Various embodiments of the invention, simply by illustrating the best mode of carrying out the invention, are as follows.

Electronically insulating proton conductor of a membrane electrode assembly capable of converting the chemical energy of a reaction into electrical energy at a temperature of 220 ° C to 550 ° C. An electronically insulated proton conductor of a membrane electrode assembly capable of converting the chemical energy of the reaction into electrical energy at a temperature of about 175 ° C to about 550 ° C, an electronically insulating proton conductor comprising an acid-free liquid phase.

A proton conductive composite membrane comprising an electronically insulating proton conductor of a membrane electrode assembly capable of converting a chemical reaction response into electrical energy at a temperature of about 220 ° C to about 550 ° C. able to convert chemical energy

I »Φ · ♦ · * * Φ Φ

Reaction to electrical energy at a temperature of about 175 ° C to about 550 ° C, an electronically insulating proton conductor containing no acid, to maintain conductivity.

A membrane electrode assembly comprising an electronically insulating proton conductor and capable of converting the chemical energy of a reaction into electrical energy at a temperature of about 220 ° C to 550 ° C. The membrane electrode assembly comprising an electronically insulated proton conductor and which is capable of converting chemical energy reactions into electrical energy at a temperature of about 175 ° C to about 550 ° C, the membrane electrode assembly does not contain acid to maintain conductivity. The membrane electrode assembly may have a surface area resistivity in the range of about 0.01 to 100 ohm.cm ² .

The membrane electrode assembly may include a metal hydride support and an electronically insulating proton conductor on the metal hydride support. The electronically insulating proton conductor can be catalyzed.

Another embodiment is a fuel cell comprising an electronically insulating proton conductor, the fuel cell being capable of converting the chemical energy of the reaction into electrical energy at a temperature of about 220 ° C to about 550 ° C. Yet another embodiment is a fuel cell comprising an electronically insulating proton conductor, the fuel cell being capable of converting the chemical energy of a reaction into an electrical one. energy at a temperature of about 175 ° C to about 550 ° C, an electronically insulated proton conductor containing no acid to maintain conductivity. The fuel cell may comprise a metal hydride or a mixed conductor capable of conducting electrons and protons. The fuel cell may comprise a reforming catalyst.

Another embodiment is a fuel cell, comprising electrodes and means susceptible to exposure to at least one chemical, for use in the treatment of at least one chemical. 94 conversion of chemical energy into electrical energy at a temperature of about 220 ° C to 550 ° C. Yet another embodiment is a fuel cell comprising electrodes and means susceptible to exposure to at least one chemical, to convert chemical energy to electrical energy at a temperature of about 175 ° C to about 550 ° C, an electronically insulated proton conductor containing no acid to maintain conductivity . The fuel cell may comprise a membrane electrode assembly, has a specific surface area resistivity having a thickness of about 175 microns, and a proton conductivity within the gap of FIG. 1 or FIG.

2.

One embodiment is an electricity generating system comprising a fuel reformer and a fuel cell, the fuel cell being capable of converting chemical reaction energy into electrical energy at a temperature of about 220 ° C to about 550 ° C. Another embodiment is an electricity generating system comprising a fuel reformer and a membrane electrode assembly comprising an electronically insulating proton conductor, the membrane electrode assembly being capable of converting chemical energy into electrical energy at a temperature of about 175 ° C to about 55 ° C, an electronically insulating proton conductor. containing no acid to maintain conductivity. In the system, the fuel reformer may be a synthetic gas generator. The fuel reformer may comprise a reforming catalyst in the fuel cell and / or an external reformer. The synthetic gas generator is capable of generating hydrogen. The system may further comprise a water gas conversion reactor and / or an oxidation unit.

Electronically insulating proton conductor is selected from the group consisting of Ba ₃ Ca1.1eNb1.82Oe.73 - _H2O (BCN 18; CSH ₂ PO ₄ (CDP) Sr [Zr .9Yo.i _0] 0 ₃ -S {SZYO) ; polyphosphate compounds containing

19.96% wt. NH ₄ ⁺ , 29.3%. P, 1.51 wt. Si; La ₀ . ₉ Sr ₀ .iSCo.9Mgo.i

• * ♦

0 ₃ (LSSM); ₀ .9 and BACE-x Zr _x Mo.iO3-6 / wherein M is Gd or Wd and x = 0 to 0.4 (BCZMO). In the proton conductive composite membrane, the metal hydrides are selected from the group consisting of Pd and Pd alloys, V / Ni / Ti, V / Ni, V / Ti, PdAg, PdCu, Ti, LaNi ₅ , TiFe and CrV ₅ . The anode A / or cathode may comprise a noble metal and / or a non-noble metal. The anode and / or cathode may comprise a layer which permits gas diffusion and electron conduction. The layer is selected from the group consisting of carbon fabric and metal fabric.

Another embodiment is a method of converting a chemical energy reaction into electrical energy, comprising exposing the electronically insulating proton conductor to a chemical at a temperature of about 220 ° C to about 550 ° C and generating an electromotive force (emf) through the electron insulating proton conductor. Yet another embodiment is a method of converting a chemical energy reaction into electrical energy comprising exposing an electronically insulating proton conductor to a chemical at a temperature of about 175 ° C to about 550 ° C and generating an electromotive force (emf) through the electron insulating proton conductor; wherein the electronically insulated proton conductor contains no acid to maintain conductivity. The methods may further comprise exposing the electronically insulating proton conductor to an oxidizing agent and / or forming a chemical by reforming another chemical.

Another embodiment is a method of manufacturing a membrane electrode assembly comprising applying a precursor from an electronically insulated proton conductor to a mixed conductor capable of conducting electrons and protons and heating the precursor to convert the precursor into an electronically insulating proton conductor, wherein the membrane electrode assembly is capable of altering the chemical energy of the reaction. to electrical energy at a temperature of about 220 ° C to about 550 ° C. Yet another embodiment is a method of manufacturing a diaphragm electrode assembly, comprising a diaphragm electrode assembly, comprising: a. Applying a precursor from an electronically insulated proton conductor to a mixed conductor capable of conducting electrons and protons and heating the precursor to convert the precursor to an electronically insulating proton conductor, wherein the membrane electrode system is capable of changing the chemical energy of the reaction to electrical energy at temperature of about 175 ° C to about 550 ° C, the electronically insulated proton conductor contains no acid to maintain conductivity. The precursor is applied by brushing or by air application. The mixed conductor is Pd foil. The precursor is heated in an NH ₃ atmosphere. The heating is at a temperature in the range of about 100 ° C to about 600 ° C, preferably in the range of about 100 ° C to 400 ° C.

The method of manufacturing an MEA may further comprise preparing an electronically insulating proton conductor, catalyzing the membrane electrode assembly, wherein preparing the electronically insulating proton conductor comprises preparing the silica particles, preparing the polyphosphate, and mixing the silica particles and the polyphosphate to prepare the precursor.

In the products and methods of the invention, the membrane electrode assembly is capable of converting a chemical reaction energy into electrical energy at a temperature of about X ° C to about Y ° C, where Y is

larger than X a X and Y are elected from the group containing 220, 230, 240, 250, 260, 270, 280, 290, 300 , 310, 320, 330 350, 360, 370, 380, 390, 400, 410, 420, 430 , 440, 450, 460, 470 480, 490, 500, 510, 520, 530 a 540.

Also in the products and methods of the present invention, a membrane electrode assembly capable of altering the chemical energy response to electrical energy at a temperature of X ° C to about Y ° C, wherein Y is greater than X and X and Y are selected from the group consisting of 175 , 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 4, 7, 8, 9, 10, 11, 12, 13, 14 · · Φ · 4 · · 4 · 4 · 44 · 4 · · 44 ·

310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430

440, 450, 460, 470, 480, 490, 500, 510, 520, 530 and 540, the electronically insulated proton conductor contains no liquid phase-containing acid.

As explained above, conventional MEA uses Nafion as EIPC. The Nafion proton conductivity decreases monotonously as the temperature rises above 100 ° C. Conductivity can be maintained by increasing the pressure, thereby increasing the boiling point of the water and maintaining the hydration of the membrane. This is an energy-intensive proposal.

While conventional fuel cells use Nafion or acids that exhibit a loss of proton conductivity within the gap region of Fig. 1, the high temperature MEA electrolyte of the present invention has proton conductivity within the gap region of Fig. 1 which increases monotonously as the temperature rises above 100 ". 0. Similarly, unlike other competing electrolytes, polybenzimidazole with phosphoric acid (PBI) admixture, because although the acid-added PBI is unstable above 250 ° C, the proton conductivity of the high temperature MEA electrolyte described in the present invention continues to rise to above 400 ° C. The difference between the high temperature electrolyte system MEA described in the present invention and Nafion or PBI (both polymer electrolytes) is that. that the high temperature electrolyte MEA does not require (a) humidification, whereas Nafion does, or (b) phosphoric acid or other free acid that PBI needs to maintain conductivity.

What is needed in the art in the long term are MEAs for higher temperatures. MEAs operating at or above 150 ° C alleviate CO poisoning of the anode catalysts. MEAs operating above 300 ° C eliminate the need for WGS reactors and preferential oxidation units.

9 ··· ··· · 9

9,999,999 9,999,999 9

9 9 «9 9999

98 «9 9 · * 9«

This results in a much more compact system and allows the introduction of partially reformed methanol into the medium temperature fuel cell. High temperature fuel cells in this context are defined as fused carbon fuel cells operating at 650 ° C, while low temperature fuel cells are defined as fuel cells operating below 100 ° C {e.g. hitherto known fuel cells with polymer electrolyte). Medium temperature fuel cells are the essence of this patent application. For purposes of this application, a preferred medium temperature fuel cell mode is 150 ° C to 400 ° C. This temperature mode includes temperatures at which methanol internal reforming can be conducted within the fuel cell field flow. The advantage of the high temperature electrolysis system is that it eliminates the need for bulky WGS and PROX reactors.

The problem of being unable to prepare robust membranes from EIPC as described in the reference to Norby is solved by using a proton-guiding carrier. In this patent application, the carrier is referred to as component D. Metal hydride films comprise materials such as Pd,

PdAg, PdCu, Ti, LaNi ₅ , TiFe and CrV ₂ are very robust and can serve as fuel and oxidizing agent separators even with substantial pressure differences. These materials in turn absorb hydrogen. Hydrogen atoms can diffuse from the surface to the volume and move to intermediate positions of tetrahedra or octahedron. Absorption of hydrogen into the bulk of these materials results in hydride formation. These metal hydride films are dense phases that allow hydrogen atoms to diffuse therethrough, since they are electron conductor membranes, they must be facing with EIPC layers. However, since the metal hydride foil serves as a carrier and separator, the need for robust films for inorganic EIPC is eliminated. The EIPC layers need to prevent the fuel cell current collectors from touching the electronically conductive metal foil (or component D). Therefore, it is not possible to use a metal hydride foil as a carrier for a high-temperature Β Β · · · · · · · · · · · · · ·

Β Β Β A Β Β «ΒΒΒ

BB BB BB Β Β · · Β

EIPC that cannot be manufactured into robust membranes. We choose proton conductors from metal hydride for the following reason. When protons are discharged from the catalytic surface of the anode, protons can chemisorb as hydrogen into the metal surface. In order to keep the hydride system neutral, protons are ejected from the opposite surface of the two-dimensional film. Chemisorbed hydrogen can diffuse into the metal volume and diffuse through the film to the opposite side. As hydrogen diffuses to volume, it is replaced by newly chemisorbed hydrogen as the anode continues to form more protons. Protons are formed when molecular hydrogen is divided into two electrons providing two protons that penetrate the membrane electrode assembly and two electrons that are discharged into the outer circuit. The Pd metal has an fcc (area center cubic) system with a spatial lattice parameter of 0.3887 nanometers. Upon hydrogen absorption, the lattice expands isotropically and retains the fcc system. At low hydrogen equilibrium pressure, hydrogen dissolves in the diluted and phase.

When the H / Pd ratio is 0.015 at 298 ° K, Pd becomes the β phase of the hydride when the grid parameter is 11% higher than the metal grid parameter.

This increased grid parameter causes hydrogen diffusivity to increase. Hydrogen diffuses relatively rapidly into Pd. This phenomenon is what allows the use of Pd as a carrier for the production of composite systems that can serve as membrane electrode assemblies for fuel cells.

It is a feature of the high temperature MEA electrolytes described herein that there is no need to add any liquid phase (eg, water or free acids) to maintain the proton conductivity.

The properties of the high temperature electrolyte of the MEA system can be quantified as follows:

(1) Conductivity increases when the temperature rises above 100 ° C.

• ·· · ΦΦΦ φφ I · Φ ΦΦΦ · φ · · · φ · φ ΦΦΦ ΦΦΦ «

(2) No additional liquids need to be added to maintain conductivity.

(1) High temperature membrane electrolyte system

An example of a high temperature electrolyte MEA is shown in FIG.

3, wherein a non-polymer medium temperature fuel cell is schematically illustrated. This diagram is not to scale. The Pd film used for component D was 25 μπι thick.

In this scheme, the composite C / D / C system constitutes the EIPC. Components C and D are both proton conductors, also called proton conductors. When component D is also an electron conductor, a multi-layer system may be required. Components C are EIPC layers which are serially interfaces to D. The C / D composition is, in particular, an EIPC composition that conducts protons and therefore, an electronically insulating proton conductor.

In Fig. 3, component A is a porous gas diffusing layer and component B is an electrocatalytic layer. Among the various embodiments of component A that may be used in the present invention are carbon papers, carbon fabrics, metal screens or each electronically conductive porous material. The purpose of component A is to serve both as a current collector and as a diffusion layer which allows the fuel gas to diffuse through the catalytic layer. among several embodiments of component B that may be used in the present invention are noble metals such as Pt, Pd, Ru, single phases and mixed phases containing the above noble metals and nickel, chromium, molybdenum, osmium, rhodium, iridium, rhenium, and single phases and mixed phases containing all the above components.

One embodiment of the high temperature electrolyte is schematically designated C / D / C. When high temperature electrolyte is catalysed 9 9 9 9 9 9 9 9 9 4 9 99 4 4 99 99 catalytic layers (Β), the system is schematically designated as B / C / D / C / B and will be referred to as an MEA design.

Another embodiment is a two-layer electrolytic system wherein D is an electron conductive proton conductor and C is an EIPC. A scheme of such a system will be (a) C / D or (b) D / C wherein u (a) the anode catalyst layer is in contact with the EIPC layer and (b) the cathode catalyst layer is in contact with the EIPC. The complete schemes of these two options are:

(a) Banode / C / D / B _cathode (b) B _anode / D / C / B _cathode

In the above two cases (a) and (b), the D / C or D / C compositions are both EIPC compositions because layer C blocks electron conductivity through the composition.

One method of producing the high temperature electrolyte MEA shown in Figure 3 is as follows.

The first dense phase of the proton-permeable material must be selected as part of D. The term dense phase of the proton-permeable material is any material that is proton-permeable but not permeable for chemical classes higher than atomic hydrogen. The carrier for the EIPC layers is part D. The carrier is permeable to hydrogen atoms. The carrier should not be an electron insulator and is preferred when not. The carrier is hydrogen permeable and stable at temperatures in excess of 350 ° C. The carrier is a two-dimensional stable membrane capable of serving as a carrier for EIPC materials. When the support is electronically insulated, no additional EIPC is needed. Examples of carriers include Pd, Pd alloys and vanadium alloys.

• «fcfc fc ··· fcfc fc fc fc ·» · fcfc · fcfcfcfc · fc «·« · · fcfcfc fcfc ·· • fc fcfc fcfc · fcfc · «

In one embodiment of the invention, the dense phase proton permeable material comprises a metal hydride sheet. An example of a metal hydride film is Pd. Other examples include Pd alloys (eg, PdAg alloys) and V / Ni / Ti, V / Ni, V / Ti, where V is vanadium, Ni is nickel, and Ti is titanium. These materials form part D. The film thickness of part D could be in the range of 5 to 1000 gm and more preferably in the range of 10 to 200 gm, and most preferably in the range of 20 to 100 gm. In one example, the Pd film thickness was 25 gm.

Second, the interface of component C with one or both surfaces of component D forms a composite electrolytic system. The selection of part D is followed by the choice of EIPC material (part C). The component C is then glued or applied to one or both surfaces of the component D to form two layers or two layers. three-layer electrolyte.

EIPC is any material capable of conducting protons but which is electronically insulating. Electronically insulating means that it does not conduct electrons. Low temperature EXPCs may contain Nafion, PBI alloyed phosphoric acid, and each proton-conductive polymer. High temperature EIPCs are usually inorganic or compounds of inorganic materials and polymeric (organic) binders. Examples of inorganic and composite organic / inorganic systems include:

Inorganic water systems:

1. Mesoporous zirconium phosphate pyrophosphate Zr (P ₂ O ₇ ) ₀ . _e i

Superprotonic water of non-stoichiometric phase M ₂ H _y (AO ₄ ) ( _{X + y} ) · χΗ ₂ 0. Ba ₃ Cai, and Nbi.e2O8.73 ₈ ^- H ₂ O

4. Cs _with H ₃ (SO ₄ ) ₄ * 0.5 H ₂ O

5. Organic-inorganic hybrid (ICS-PPG), composed of

3.Iisocyanato propyl-triethoxysilane (ICS) and glycol) bis- (2-amino-propylether) (2-APPG), poles (propylene mixed with peroxy-tungstic acids)

PTA / ICS-PPG)

6. Hydrates of SnCl ₂ • · · 4 • 4 444 4 * * • 4 44

4 4 4 4

4 ···· 444 ·

Β

4 44 (W-PTA), (abbreviated WAinorganic systems without water

1. Silver iodide quatungstate Ag ₂₆ Ii _B W ₄ 0i _e

2. CSi-xd1HJxHaPCU, Csi- _X (ND ₄ ) _X D ₂ PO ₄ and Κ !. _Χ (ΝΗ ₄ ) _Χ Η ₂ ΡΟ ₅

KH ₂ PO ₄

4. Tetraammonium dihydrogen triselenate (NH ₄ ) ₄ H ₂ (SeO ₄ ) ₃ CsDSO ₄

The materials used for component C set the high temperature limit of operation of the high temperature electrolyte MEA. The part material can be selected from: Ba ₃ Cai. NBI _{18, 82 O-B} .73 _H2O (BCN 18); CsH ₂ PO ₄ (CDP); SrfZro.gYo.iJOs-stSZYO); % polyphosphate compound containing 19.96 wt. P, 1.51 wt. Si; Lao.9Sro.jSco.9Mgo.1O3 (LSSM); and

BaCeo.9- _x Zr _x M ₀ .i0 ₃ -s wherein Gd or Wd and x = 0 to 0.4 (BCZMO). All of these materials of component C are capable of operating at temperatures within the gap of Figure 2.

Component C is adhered or applied as a film to component D at a thickness such that the EIPC composed of C and D has proton conductivity within the gap region of Figure 2. The conductivity units are S / cm where S is Siemens. Siemens is the inverse of ohm (ie l / Ω). The conductivity of the material is an intrinsic property of the material.

The Pd film has an increasingly higher conductivity as the temperature rises, as the grid expands and the hydrogen permeability increases. However, whenever a layer is added in series the resistance always increases. However, once one component has a significantly higher resistance, then the series resistance is essentially the resistance of the material having the higher resistance. The component with the highest resistance will be components from the EIPC. When part C of the layer C is in contact with the layer C flat to the film, the C / D composition will be at least as good as Nafion. The calculations will determine the thickness that will be required to do so. Another way to look at it is as follows. What happens to the resistor when Pd is added to the EIPC? At the highest temperature, the increase in resistance will be negligible. At the lowest temperature, the resistance of the composition will be slightly higher than the resistance of the EIPC film itself. However, the EIPC will be a limiting resistor at the temperature within the gap region of Figures 1 and 2 when fuel with high hydrogen partial pressure is fed to the anode current of the fuel cell containing the C / D composition.

The EIPC material, i.e., part C, is in contact with the metal hydride sheet serving as a binder material. The binder material may be inorganic or organic. Polybenzimidazole (PBI) is stable above 300 ° C unless soaked with phosphoric acid. The dissolved PBI polymer may be contained in an EIPC dispersion. This dispersion is referred to as EIPC ink. The ink is applied to the metal hydride foil and the composition is heat treated. The ink preparation may be optimized for each selected EIPC and for each selected component D. Alternatively, the EIPC vapor layer may be deposited on the surface of component D. The steam deposition methods used include vacuum deposition methods as well as atmospheric pressure deposition methods.

The electrolysis system is then catalysed on both faces of the electrolysis system. When a two-layer or three-layer composite system is prepared, the outer surfaces are catalyzed by the anode catalyst on the fuel side and the cathode catalyst on the side of the oxidizing agent. The anode materials may include precious metals, precious metal alloys, and mixed phase mixed metal catalysts. The cathode side may contain precious metals, in which the precious metals may be present. Mixed metal catalysts, transition metal catalysts, ruthenates, pyrochlores and other catalytic materials.

The result is an MEA system whose use and performance will be described below using the MEA system in the partial reformate fuel cell shown in Figure 5.

(2) Partial reformate fuel cell

The aforementioned MEA can be directly incorporated into the fuel cell. The use of the high temperature components C gives the high temperature membrane electrode assembly described in this application as a high temperature electrolyte MEA system. The metal hydride component D is not a limiting factor with respect to temperature, as this material can withstand higher temperatures than component C (e.g., greater than 1000 ° C).

The basic physical structure or fuel cell building block comprises an electrolyte layer in contact with the porous anode or cathode on opposite surfaces of the electrolytic system. A schematic representation of the reagent fuel cell / product gases and ion flow directions through the cell are shown in FIG.

5. In a typical fuel cell, the gas fuels are fed continuously to the anode (negative electrode) space and the oxidizing agent (ie, oxygen from the air) is continuously fed to the cathode (positive electrode) space; an electrochemical reaction occurs at the electrodes to produce electric current.

MEA is incorporated into the fuel cell hardware. The technical equipment may comprise bipolar plates with a fuel diaphragm on the anode side and an air plenum on the cathode side.

These plates are electronically conductive plates having grooves (i.e.

9 9

99999 9 9 to direct the fuel and oxidant to the anode and resp. cathode. Further, these plates conduct electricity to the next cell in series in the stack. The flow field regions (also known as outer or highest flow field areas) are in contact with the gas diffusing layer (eg, component A of Figure 3). The component A is then in contact with the catalytic layers (layers B). The catalytic layers directly contact either layer C or layer D. Further details of the fuel cell hardware can be obtained from Fuel Cell Handbook, 4 edition, published by the USDepartment of Energy, Office of Fossi Energy, Federal Energy Technology Center, Morgantown, WV. Pitsburg, PA available at www.fetc.doe.gov. which is incorporated herein by reference.

TYPY- ^which can use high temperature electrolyte MEA contains the following types:

(1) In a free-standing fuel cell or fuel cell stack.

(2) In the fuel cell with reforming catalysts in the bipolar plate flow fields.

(3) In a fuel cell thermally integrated with an external reformer having a reformer, a preferential oxidation unit and a water gas conversion reactor.

(4) In a fuel cell thermally integrated with the reformer only.

(5) In a fuel cell with reforming catalyst in the flow fields in combination with an external fuel processor, wherein the fuel processor comprises a reformer, a water gas converter, and a preferential oxidation unit.

(6) Regenerative fuel cells.

(7) Electrochemical organic chemical transformation reactors.

4 9 99 · 9 9 9

9,999 «9,999,999 9 9 9 9 • 9,999« 9999

93 9 · 9 ·· β *

Fuel cells using a high temperature electrolyte will be much better than the known polymer electrolyte fuel cells because the operating temperature is higher. High temperature operation will improve the performance of the cathode side as the cathode kinetics (oxygen reduction) improves with increasing temperature. This is a characteristic of Arhenia's kinetics. Also, the anode performance will be increased because CO poisoning of the anode catalyst is alleviated by the operation being carried out at high temperature. If components C that are stable at temperatures above 250 ° C are used, methanol can be reformed directly in the fuel cell as well as in an external reformer. Since the fuel cell operates at a higher temperature, thermal integration of the fuel cell with the fuel processor (e.g., a methanol reformer) is facilitated. When the fuel cell is operated at 150 ° C, CO poisoning is alleviated, but internal reformation cannot be selected.

A fuel cell according to one embodiment of the present invention is shown in Fig. 6.

The preparation of the fuel cell components and one embodiment of the fuel cell of the present invention will be described below.

(A) Preparation of EIPC

The components of EIPC are ammonium polyphosphate and silicon dioxide. Ammonium polyphosphate and silica are prepared separately and then blended to form a mixed EIPC material as described below.

(i) Preparation of silica

The preparation of the silica particles is based on the chemical reaction of tetra-esters of silicic acid (tetraalkyl silicate) in solutions containing methanol or ethanol or other alcohols.

«4 * 4 * 44 * 4 * * * 4» 44 4

4,444 4,444 * * 4,444 44,444 4 *

The formation of silica particles by the reaction of tetraethyl silicate in a solution of water in the presence of certain bases is described in Kolbe, G., Das complexchemische Verhalten der Kiesselsaure, dissertation, Jena (1956). The method used in this embodiment is the Stober-Fink.Bohn method described in Werner Stober, Arthur Fink and Ennst Bohn, Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range, Journal of Colloid and Interface Science 26, 62-69 (1968). ).

The reagents required to form the silica of one embodiment of the present invention are as follows:

Methanol, ethanol, n-propanol and n-butanol, which are of analytical reagent quality and are used as solvents;

silicic acid tetraesters (tetraalkyl silicates) of technical grade (eg tetramethyl silicate, tertraethyl silicate, etc.);

anhydrous ammonia (99.9% purity); and ammonium hydroxide, 26 ° Be (Baumé) for the United States Pharmacopeia grade.

Pure alcohol or a mixture of alcohols, saturated ammonia in alcohol solution, ammonium hydroxide and water were mixed in an Erlenmeyr flask (reaction vessel) with a ground stopper or rubber sealed injection flask at the desired ammonia-water concentration. 1 mol-mol of ammonia was used as a catalyst to form spherical silica particles. It was added to the alcohol mixtures by adding saturated alcoholic ammonia solutions to the reaction vessel. When high concentrations of ammonia were desired in alcoholic mixtures, a saturated ammonium hydroxide solution was used. The concentration of ammonia in the mixture of alcohols was measured by drawing off small samples and titrating with 1N hydrochloric acid. The total water content was calculated by adding the fractional amounts of water introduced into the reaction vessel by all components.

4 4 4

4445 · 4

4 4 4 4 * 4 444 4 4 • 4 4 44 4 4 44

4 * 44 44

The alkyl silicate was then added to the reaction vessel, mounted either on a shaker or in an ultrasonic water bath. After an initial phase of invisible silica-forming hydrolytic reaction, a second phase, the condensation of the supersaturated silica, was found by increasing the opalescence of the mixture, which began 1 minute to 5 minutes after addition of the tetraalkyl silicate. Process diagrams illustrating the first and second phases of the reaction are shown in Figure 7. The white silica slurry is then filtered off the solution.

(ii) Preparation of ammonium polyphosphate

Phosphorus pentaoxide 98% pure, ACS class (American Chemical Society), was added to phosphoric acid (85 wt%, ACS class), grams of phosphorus pentaoxide (P ₂ O ₅ ) and 4.64 ml of phosphoric acid were mixed in 250 ml beakers at room temperature. 4.64 ml of phosphoric acid was based on the following calculations:

The number of moles of 98% pure P ₂ O _{5 = (10 * 0.98) /} 142 = 0.069 moles.

Number of moles of phosphoric acid = 0.069 moles;

Basicity of phosphoric acid = 3

The normal concentration of phosphoric acid is known to be 44.6 N

Molarity of phosphoric acid = 44.6 / 3 = 14.866 M = 14.866 mol / liter

Phosphoric acid volume = 0.069 / 14.866 = 4.64 ml

A magnetic stir bar was placed in a beaker. An oil bath (DirecTorr Gold Vacuum Oil Pump - Welch, vapor pressure @ 25 ° C is 5 * 10 ⁷ Torr) was prepared on a hotplate and kept at 200 ° C. A beaker of P ₂ O ₅ and phosphoric acid was placed in a bath and stirred continuously until all of the P ₂ O _{5 was} completely dissolved to form phosphoric acid (HPO ₃ ). Temperature

9 * 99 9 · · · · 9 · 999 9 9 ·

9 9 9 9 9 · 9 9 9 * 9 · 9 · 9 · The bath was reduced to 150 ° C and excess urea 99% + purity, grade ACS, in a 2: 1 molar ratio and phosphoric acid, was slowly added into a beaker with constant stirring. The urea addition was carried out slowly over a period of about 45 minutes so as not to foam as a result of CO ₂ release. Crude polyphosphate was formed in the beaker.

The crude polyphosphate was purified as follows. The crude polyphosphate was dissolved in hot water, which was then cooled to room temperature. An equal amount of methanol was added to precipitate the polyphosphate. The white polyphosphate crystals were collected in about 1 hour and filtered using a Millipore filter pump (Micron Separations Inc. Magna Nylon, Supported Plain, 0.45 micron filter papers). The white powder was dried under vacuum at about 120 ° C for about 2 hours and then baked in a tube furnace (Thremolyne, Model # 21100) under ammonia atmosphere at 300 ° C for 20 hours to complete the reaction of any residual polyacids to ammonium phosphate. The X-ray diffraction pattern of the final product confirmed that it was ammonium phosphate.

(B) Preparation of the EIPC

An EIPC according to an embodiment of the invention is a compound obtained by melting a mixture of polyphosphate and silica at nanoscale (490 nm) at 400 ° C for 20 hours in an ammonia atmosphere (Cl ... preparation of MEA

In one embodiment, the MEA comprises an electrochemically processed Pd film having an EIPC on the cathode side. Giant. 8 shows a Pd foil with five layers of EIPC on one side, suspended on a frame stand after 20 hours of firing in an atmosphere tttttt tttttt ··

4 · ··

NH ₃ . This embodiment is referred to as Pd / ElPC. The Pd / ElPC is then sandwiched between two catalyzed gas diffusing layers as shown in Figure 6.

(i) Preparing the Pd film

A 0.001 inch thick palladium film, obtained from Johnoson Matthey, was cut into 3.5 x 3.5 cm ² square pieces. It was then flamed using a hydrogen torch and pressed between two stainless steel sheets using a Carver press of 1800 kg (1800 lb) to make the film soft and flat. Four small holes were punched in the corners.

A solution of _PdCl2 50 g / 1 _NH4 C1 30 g / 1 HCl was added to form a solution of pH from 0.1 to 0.5 as specified in the publication PALLADIUM AND PALLADIUM-ALLOY PLATING, Ronald J. Morrisey, edited by Michael Murphy, METAL FINISHING 2000 Guidebook and Directory Iasue, January 2000, Volume 98, Number 1, pp. 289-290.

Pd The film was hung on a hook made of Pd wire, which also served as a working electrode lead and immersed in a Pd solution. Another Pd wire was used as a counter electrode. A 0.1 A plating current was applied for 20 seconds on both sides of the Pd Film using a potentiostat (VersaStat ™ from G&G Princetown Applied Research).

The palladium-coated film was rinsed and suspended on a home-made frame at four corners with thin copper wire to prevent the film from curling during heating.

(ii) Applying the EIPC to the cathode side of the film to to to this to to to ** to to

EIPC and silica gel were mixed in a 4: 1 molar ratio. The 4: 1 ratio was based on the stoichiometric reaction:

4 (NH ₄ ) ₂ HPO ₄ + SiO ₂ - (NH ₄ ) ₂ SIP ₄ 0i3 + 6NH ₃ + 5 NH ₃ + 5 H ₂ 0

Methanol was added and the suspension was constantly stirred to prevent the deposition of EIPC and silica. The slurry was applied by air using Aztek, model A320, air dispensing equipment, to one side of the Pd film under an infrared lamp so that methanol could evaporate rapidly and the EIPC and silica gel could be dispersed uniformly over the Pd film.

Once one layer was dispersed, the Pd film was baked in an oven under an atmosphere of NH ₃ at 400 ° C for two hours and then cooled to room temperature. The second layer was then sprayed with air onto the first layer and then sintered in ammonia at 400 ° C for 2 hours. This process was repeated until 4 layers were sprayed. After deposition of the fifth layer, the Pd film was subjected to baking in an NH ₃ atmosphere at 400 ° C for 20 hours. It was then reduced to 300 ° C in one hour, 200 ° C in one hour, 100 ° C in one hour and finally to room temperature.

(iii) Catalyzing EIPC on Pd film

The Pd film was sandwiched between two high temperature gaskets obtained from Dewal industry, RI. Platinum ink (Pt ink), made by mixing Pt carbon black, obtained from Johnson Matthey, fuel cell class and 10 wt. The EIPC powder with isopropanol was sprayed onto the Pd film on the EIPC layer side. Pt carbon black is a highly dispersed unsupported platinum particle with a typical surface area of 65 m ² per gram of platinum.

V 9 9 · · Β 9 99 «* 9 9« 9 9 9 9 9999 9 9 9 · (iv) Catalyst of gas diffusing layers

Elat is the brand name of the carbon fabric brand. Two-sided Elat (E-Tek, Inc.) Was cut into 2 cm squares. The total area of the squares is 4 cm ² . Bilateral Elat is a commercially available gas diffusing electrode. It consists of a woven carbon fabric of 116 g / cm ² (3.4 oz / yd ² ). The thickness of this fabric was 0.36 mm. The GDL side facing the gas side is moisture resistant due to the hydrophobic fluorocarbon / carbon layer. The commercially available Elat fabric was modified as follows. The Pt ink was then applied to one side of two Elat double-sided fabrics (ETek, Inc), each having a size of 4 cm ² . Both bilateral Elat were dried in an oven at 120 ° C for 1 hour to produce a catalytic gas diffusing layer (GDL).

(C) Fuel Cell Test (i) Fuel Cell System

Two catalyzed GDLs were placed in the gasket side window with the catalyzed side in contact with Pd / EIPC. The Pd / EIPC is inserted between two catalyzed GDLs to give a structure designated as GDL / Pd / EIPC / GDL. This composite assembly is then inserted between the PTFE gaskets with the PTFE gaskets window exposed to the GDL areas as shown in FIG.

PTFE / GDL / Pd / EIPC / GDL / PTFE is then sandwiched between two graphite blocks with flow fields cut into faces (see end blocks of Figure 6) to form a fuel cell assembly. Each graphite block is referred to as a flow field (FF). The fuel cell is designated as FF / PTFE / GDL / Pd / EIPC / GDL / PTFE / FF. The graphite blocks of the flow field of the graphite cell are mounted in the appropriate position using two rollers as alignment pins. The EIPC was placed on the cathode side.

(ii) Fuel cell operation

The fuel cell assembly was placed in a heated press (Carver Inc. Model C), with heated pusher plates, and was pressed so that the fuel cell blocks accurately touch the hot plates. Two Kapton films (trade name for polyimide) were used to electrically isolate graphite flow channels from hot press plates.

Hydrogen and oxygen streams containing 100 standard cubic centimeters per minute (sccm) of hydrogen and 180-sccm oxygen were used as the fuel stream. The fuel stream was moistened at the temperature of the sprinkler before it was fed into the fuel cell assembly by passing the fuel stream through the water reservoirs. These magazines were called sprinklers. The sprinkler is a container that is filled with water. The gas is fed to the water. The purpose of the frit is to disperse the gas into water by forming small bubbles. The gas then exits the sprinkler and is then fed to the reactor. The purpose of the sprinkler is to saturate the gas with water. The anode and cathode sprinklers were preheated to 70 ° C and the air flow rate through the sprinklers was 50 standard cubic centimeters per minute (sccm).

The operation of the fuel cell for Tests (1) and (2) described below was as follows. Nitrogen first passed to both the anode and cathode flow fields through the sprinkler. An air preheater was also used between the sprinklers and the fuel cell, which was preheated to 100 ° C. The hot plates on the anode and cathode sides of the fuel cell were heated to 100 ° C and then to 200 ° C and a 22.5 kg force (50 ° C). In the pounds (*), the fuel cell blocks have flow fields on the outer surfaces.

Test (1): The oxygen preheater was maintained at 250 ° C. Once the steady state temperature of the graphite plates of the anode flow field was reached at 200 ° C, the fuel and the oxidation stream of hydrogen and oxygen were fed to the anode and resp. the fuel cell cathode using the Unit Instrument Series 700 mass flow controllers and the DX-5 digital control unit. The Unit Instruments Mass Flow Controller and DX-5 Digital Controller were purchased from Unit Instruments, Inc. Yorba Linda, CA.

Test (2): The oxygen preheater was maintained at 250 ° C. Once the steady-state temperature of the graphite flow field blocks reached 250 ° C, the operating data as in Test (1) was reached except that the cell temperature was 250 ° C.

Fuel Cell Polarization Tests were performed for both Autolab (EchpChemie B.V.) PGSTAT potentiostat test (2) and (2). Current versus voltage curves were recorded at 200 ° C (test 1) and 250 ° C (test 2) using different potentials between 0.7 V and 0.1 V for 60 s at each potential. The following figure shows the I-V polarization curve at 200 ° C and 250 ° C. Hydrogen loses electrons on the catalytic surface of the anode. Each diatomic hydrogen molecule loses two electrons and acquires two protons. Two electrons are transferred to the outer circuit. The protons pass through the Pd film and then through the cathode side EIPC layer. The electrons pass through an external circuit where work can be performed and then onto the catalytic surface of the cathode. On the catalytic cathode surface, protons coming from the MEA, electrons from the outer circuit, and oxygen from the gas phase all se • «*

• · * ft

they combine to form water. The chemical reactions described above can be described by the following reactions:

Anode reaction: H ₂ -> 2H ⁺ + 2e '

Cathode reaction: 1 / 2O ₂ + 2H ⁺ + 2e '-> H ₂ O

The whole reaction

H ₂ + 1 / 2O ₂ -> H ₂ 0

The driving force for the above reactions is the free energy of the reaction for burning methanol with oxygen, which is a spontaneous reaction. The rate of reaction is given by current as a function of potential. The performance curves for test 1 and test 2 are shown in Figure 9.

(D) Fuel Cell Technical Data

Giant. 9 shows the fuel cell technical data curves. The data demonstrate that, according to the present invention, fuel cell power curves can be obtained at temperatures higher than phosphoric acid fuel cells and alkaline fuel cells, and still at temperatures lower than molten carbonate fuel cells. The above data also show that MEA performance improves with increasing temperatures. Prior to the present invention, no fuel cell power curves were obtained at about 250 ° C.

The conductivity of the EIPC of the fuel cell whose power curves are shown in Figure 9 is 1.0 x 10 ⁴ S / cm. From a given EIPC conductivity value, the thickness was calculated to provide a film with the selected specific area resistance (ASR). The criteria used were such that the specific MEA surface resistance was comparable to that of Nafion at 80 ° C, which has a proton conductivity similar to that of the material that will be in the region of the gaps of Figures 1 and 2. The MEA had sufficient and aaa and aaa and aaa aaaa and aaaa aa aa aa and a proton conductivity equal to Nafion at 80 ° C, as follows:

Conductivity σ (in S / cm) = L / (RA) where L is the thickness in cm, R is the resistance in Ω and A is the area in cm ² .

Specific area resistance (ASR) in D.cm ² - RA = L / σ

For Nafion 117 at 80 ° C, the instruction states an electrolyte resistance of 30 πιΩ per 5 cm ^{2 of} fuel cell.

Therefore, the ASR of Nafion at 80 ° C in normal fuel cell operation = 0.150 Ω. cm ² .

For EIPC, the thickness L was determined to meet the ASR for Nafion 117 under normal operating conditions according to the formula:

L = (ASR)

Figure 10 shows another ASR (στ.στη ² ) with an EIPC thickness in gm (microns) for a Nafion 117 @ 80 ° C membrane and an MEA from Test 2 that was tested at 250 ° C. From the IV MEA curve of Test 2 (Fig. 9), the resistance to proton conductivity was calculated from the slope of the ohmic resistance at 19 ohms. The ASR for this 76 μπτι EIPC membrane was calculated to be 75 Ω. cm ² . To meet the criterion that the ASR should be similar to that of Nafion 117 at 80 ° C, the ASR must be about 0.150 Ω. cm ² (as Nafion in Fig. 10). By reducing the EIPC thickness of the MEA membrane from Test 2 from 76 μπι (Example 1 of Figure 10) to about 0.15 μπι (Example 13 of Figure 10), this ASR criterion was met as shown in Figure 10, where ITE membrane denotes MEA from Test 2.

♦ to tot tot tot • * * * * * * * * * * * * toto toto toto toto «« ««

The thickness of the EIPC MEA area for Examples 1 are given below:

Example 1: Thickness = Example 2: Thickness = Example 3: Thickness = Example 4: Thickness = Example 5: Thickness = Example 6: Thickness = Example 7: Thickness = Example 8: Thickness = Example 9: Thickness = Example 10: Thickness = Example 11: Thickness = Example 12: Thickness = and Example 13: Thickness ^

from Test 2 and the corresponding specific resistance up to 13, which are evaluated in Figure 10,

76.2 gm; Specific surface resistance = 75.97Ω. cm ² 50.8 gm; Specific surface resistance = 50.64Ω. cm ² 25.4 gm; Specific surface resistance = 25,32Ω, cm ² 2,54 μπι; Specific surface resistance = 0.253Ω.cm ² 0.23 gm; Specific surface resistance = 0.23Ω.οιη ² 0,203gm; Specific surface resistance = 0.202Ω.σιη ² 0.178gm; Specific surface area = 0.177Q.cm ² 0.152gm; Specific surface resistance = 0.152Ω.cm ² 0.127gm; Specific surface resistance = 0.126Ω. cm ² 0.102 gm; Specific area resistance = 0, ΙΟΐΩ-cm ² 0.076 gm; Specific surface resistance = 0,076Ω.cm ² 0,051gm; Specific surface resistance = 0.051Ω.cm ²

0,025gm; Specific surface resistance = 0.025Ω. cm ² (3) Fuel cell system with partial reformate

Giant. 11 is a schematic representation of a partial reformate system wherein the fuel processor is outside the fuel cell. Giant. 11 shows a medium temperature fuel cell that supplies the reformate heat, noting the absence of WGS and PROX. The above-mentioned system is based on the structure of the high temperature membrane electrode, which can operate at a temperature of 2550 ° C to 400 ° C. This allows high-quality heat to be transferred from the fuel cell to the reformer. The reformer requires heat input because the reform reaction is endothermic. It is well known that increasing the working temperature (150 to 350 ° C) of a fuel cell reduces the catalysis requirements. Nickel can be used as the anode catalyst. The advantage of this concept is that the medium temperature fuel cell can be thermally integrated with the reformer. At sufficiently high temperatures, methanol, CO and hydrogen are all fuels. The reformer only needs to generate a sufficiently high hydrogen partial pressure to load the film. Therefore, this system eliminates the need for a drive and a PROX unit. Further, the exothermic fuel cell may transmit heat to the reformer.

The partial reformate fuel cell can be manufactured using standard technologies including fuel processors. Because the fuel cell operates at elevated temperatures, WGS reactors and PROX units can be removed. The partial reformate fuel cell of the present invention has a high temperature electrolytic system that allows the partial reformate system to operate at elevated fuel cell temperatures.

The partial reformate fuel cell of Figure 10 is used as follows. Methanol and water are fed to the reformer. The endothermic reformer is heated by combustion of unused fuel from the anode residual gas and heat transmitted from the fuel cell to the reformer. Hydrogen, CO and some unreformed methanol leave the reformer and are fed to the anode plenum of the fuel cell. Hydrogen is oxidized at the anode. CO does not poison the anode because the temperature is too high. The non-oxidized methanol and CO leave the residual gas and serve as the combustion fuel, along with the hydrogen that has not reacted to bring heat to the reformer. There is no previous case of this at the claimed operating temperature between 250 ° C and 400 ° C, since MEAs operating at this temperature range have been previously described.

Tttt tt tt ttt ttt ttt ttt ttt ttt ttt ttt ttt ttt ttt ttt

Internal reforming

The methanol is reformed at a temperature between 250 ° C and 350 ° C. Since the fuel cell of the present invention can operate at these temperatures, the methanol reforming catalyst can be included directly in the flow fields of the anode plenum. Therefore, the aqueous methanol can be fed to the anode flow field and can be converted to hydrogen directly in the flow field. When hydrogen is then oxidized at the anode, the equilibrium for the reforming reaction moves to the product side (ie more hydrogen is generated when hydrogen is consumed at the anode. The concept of inserting methanol reforming catalyst into the flow field is not new. In this industry, methane reforming catalysts are incorporated into anode flow fields, methane is internally reformed and is oxidized at the anode, attempts have been made to reform methanol internally in polymer electrolyte fuel cells, and the results were very poor because the working temperature was too low The upper limit of the working temperature has always been given by the upper limit of the polymer electrolyte Since the concept of the present invention allows the operation of the membrane electrode assembly at a higher temperature, the kinetics of the reforming process is greatly improved. the logic of internal reformation for fuel cells within the temperature gap between the molten carbonate fuel cell and the phosphoric acid fuel cell. The reform process data is shown in Figure 12, which shows that the internal reform performance is nearly the same from 200 ° C to 300 ° C at two different water methanol feed rates. Almost all of the power can be calculated according hydrogen and C0 _second

The above description is provided to enable those skilled in the art to make and use the invention and is provided in the context of a particular application and its requirements. It will also be apparent to those skilled in the art

Φ · Φ * * * * * * 9 9 9 9 9 9 · ·

It will be appreciated that various modifications of the preferred embodiments may be made and the general principles set forth herein may be applied to other embodiments and uses without departing from the spirit and scope of the invention. Accordingly, the present invention is not intended to be limited to the embodiments described, but must be within the broadest scope consistent with the principles and features described herein.

In this application some limitations of the number ranges are given. It will be appreciated by those skilled in the art that all ranges falling within said numerical ranges are included within said numerical ranges, although the exact range limitation is not explicitly stated in the description of the invention, since the present invention may be operated throughout the entire numerical ranges. Adhering to the opposite would allow the form to triumph over substance and would allow the requirement of a written description to set aside claims that can be simply narrowed during the proceedings, since the applicants have broadly described them in this application but can then narrow their claims during the proceedings. Finally, all patents and publications cited in this application are incorporated herein by reference.

Claims (57)

PATENT CLAIMS What is claimed is: 1. An electronically insulating proton conductor of a membrane electrode assembly, characterized in that it is capable of changing the chemical energy of the reaction to electrical energy at a temperature of about 220 ° C to about 550 ° C. 2. An electronically insulating proton conductor of a membrane electrode assembly, characterized in that it is capable of changing the chemical energy of the reaction to electrical energy at a temperature of about 175 ° C to about 550 ° C, wherein the electronically insulating proton conductor contains no liquid phase containing acid. 3. A proton-conductive composite membrane comprising an electronically insulating proton conductor of a membrane electrode assembly capable of changing the chemical energy of the reaction to electrical energy at a temperature of about 220 ° C to about 550 ° C. 4. A proton-conductive composite membrane comprising an electronically insulating proton conductor of a membrane electrode assembly capable of changing the chemical energy response to electrical energy at a temperature of about 175 ° C to about 550 ° C, wherein the electronically insulating proton conductor contains no acid. to maintain conductivity. 5. A membrane electrode assembly comprising an electronically insulating proton conductor and capable of changing the chemical energy of the reaction to electrical energy at a temperature of about 220 ° C to about 550 ° C. i 0 0 000 6. A membrane electrode assembly comprising an electronically insulating proton conductor and capable of changing the chemical energy of a reaction to electrical energy at a temperature of about 175 ° C to about 550 ° C, wherein the membrane electrode assembly contains no acid to maintain conductivity. • t 0 · 00 in * v · »* 0 «fr · 0 · 0 0 * 0 0000 · 0 0 0 0 0 0 <· 00 00 0 00 00 7. A membrane electrode assembly comprising a metal hydride support and an electronically insulating proton conductor on said metal hydride support. 8. The membrane electrode assembly of claim 7 wherein the electronically insulating proton conductor is catalyzed. 9. A fuel cell comprising an electronically insulated proton conductor and is capable of changing the chemical energy of the reaction to electrical energy at a temperature of about 220 ° C to about 550 ° C. 10. The fuel cell of claim 9, further comprising a metal hydride. 11. The fuel cell of claim 9, further comprising a mixed conductor capable of conducting electrons and protons. 12. The fuel cell of claim 9, wherein the fuel cell is capable of reforming a chemical to another chemical. 13. The fuel cell of claim 9 including a reforming catalyst. »··· ·· ··. . w · · · · · · · · · · · · · · · · · · · · · · · · · · · 14. A fuel cell comprising an electronically insulated proton conductor, characterized in that it is capable of changing the chemical energy of the reaction to electrical energy at a temperature of about 175 ° C to about 550 ° C, the electronically insulating proton conductor contains no acid to maintain conductivity. 15. The fuel cell of claim 14, further comprising a metal hydride. 16. The fuel cell of claim 14, further comprising a mixed conductor capable of conducting electrons and protons. 17. The fuel cell of claim 14, wherein the fuel cell is capable of reforming a chemical to another chemical. 18. A fuel cell comprising electrodes and means susceptible to exposure to at least a chemical for converting a chemical energy reaction into electrical energy at a temperature of about 220 ° C to about 550 ° C. 19. A fuel cell comprising electrodes and means susceptible to exposure to at least a chemical to convert chemical energy into electrical energy at a temperature of about 175 ° C to about 550 ° C, wherein the electronically insulating proton conductor is free of acid, to maintain conductivity. 20. An electricity generating system comprising a fuel reformer and a fuel cell, wherein the fuel cell is capable of converting chemical reaction energy into electrical energy at a temperature of about 220 to about 550 ° C. 4 44 4 4 4 4 · · 4 4 «* 4 44 · 4 4 4 * 444 4 4 4 4 4 44 44 ·· · 21. The system of claim 20, wherein the fuel reformer is a synthetic gas generator. The system of claim 20, wherein the fuel reformer comprises a reforming catalyst in the fuel cell and / or an external reformer. 23. The system of claim 20, further comprising a water gas conversion reactor. 24. The system of claim 23 comprising an oxidation unit. 25. An electrical generating system comprising a fuel reformer and a membrane electrode assembly comprising an electronically insulated proton conductor, wherein the membrane electrode assembly is capable of changing the chemical energy of the reaction to electrical energy at a temperature of about 175 ° C to about 550 ° C. wherein the electronically insulated proton conductor contains no acid to maintain conductivity. 26. The system of claim 25, wherein the fuel reformer is a synthetic gas generator. System according to claim 25, characterized in that the fuel reformer comprises a reforming catalyst in the fuel cell and / or an external reformer. 28. The system of claim 25, wherein the synthetic gas generator is capable of generating hydrogen. * Ϊ «« »• • • • • • • • • •« «« «« «« «« «« « 29. The system of claim 25, further comprising a water gas conversion reactor. 30. The system of claim 29, further comprising an oxidation unit. 31st electronically insulating proton conductor of claim 1 or 2, characterized in that it is selected from the group consisting of Ba ₃ Cai.ieNbi.82 08.73 - _H2O (BCN 18); CsH ₂ PO ₄ (CDP); Sr [Zr _{0th 9} Y ₀ , i] O ₃ . ₅ (SZYO); % polyphosphate compound containing 19.96 wt. NH ₄ ⁺ , 29.3 wt. P, 1.51 wt. Si; La ₀ . ₉ Aug ₀ .iSco. ₉ Mgo · O ₃ (LSSM); and BaCeo. ₉ . _x Zr _x M _{0 10} -5, where M is Gd or Wd and x = 0 to 0.4 (BCZMO). 32. The proton-conductive composite membrane of claim 3 or 4, further comprising a metal hydride substrate. 33. The proton conducting composite membrane of claim 32, wherein the metal hydride is selected from the group consisting of Pd, a Pd alloy, V / Ni / Ti, V / Ni, V / Ti, PdAg, PdCl, those _with Lania, TiFe and CrV ₂ . 34. v y System znače membrane electrodes according to further comprising Claim 5, 6 or 7 anode a cathode. 35. System membrane electrodes according to claim 34, v y metal labeled by: and / or a non-precious metal. anode and / or cathode contain e rare 36. System membrane electrodes according to claim 34, characterized in that the anode and / or capable of diffusing gas and conducting electrons. cathode contains layer Φ φ φ · · · · · · φ φ φ φ φ φ φ φ φ φ φ φ 37. The membrane electrode assembly of claim 36, wherein the layer is selected from the group consisting of a carbon fabric and a metal fabric. 38. A method of converting a chemical energy reaction into electrical energy, comprising exposing an electronically insulating proton conductor to a chemical at a temperature of about 220 ° C to about 550 ° C and generating an electromotive force (emf) through the electron insulating proton conductor. 39. The method of claim 38, further comprising subjecting the electron insulating proton conductor to an oxidizing agent. 40. The method of claim 38, further comprising forming a chemical by reforming another chemical. 41. A method of converting a chemical energy reaction into electrical energy, comprising exposing an electronically insulating proton conductor to a chemical at a temperature of about 175 ° C to about 550 ° C and generating an electromotive force (emf) through the electronically insulating proton conductor. the conductor contains no acid to maintain conductivity. 42. The method of claim 41, further comprising subjecting the electron insulating proton conductor to an oxidizing agent. • · « · To «tot tot tot tot tot * * to to to to to to to to 43. The method of claim 41, further comprising forming a chemical by reforming another chemical. 44. An electronically insulating proton conductor of a membrane electrode assembly, characterized in that it is capable of converting the chemical energy of the reaction into electrical energy at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X and Y are selected from the group consisting of 220,230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350 , 360, 370, 380, 390, 400, 410, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530 and 540. 45. An electronically insulating proton conductor of a membrane electrode assembly, characterized in that it is capable of converting the chemical energy of the reaction into electrical energy at a temperature of about X ° C to about Y ° C, where Y is greater than X, and X and Y are selected from. groups containing 175, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330 340, 350, 360, 370 380, 390, 400, 410, 420, 430, 440, 450, 460 470, 480, 490 500 510, 520, 530 and 540, wherein the electronically insulated proton conductor does not contain an acidic liquid phase. 46. A proton conductive composite membrane comprising an electronically insulating proton conductor of a membrane electrode assembly capable of converting the chemical energy of a reaction into electrical energy at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X is and Y are selected from the group consisting of 220,230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 410, 420, 430 440, 450, 460, 470, 480, 490, 500, 510, 520, 530 and 540. 47. A proton conductive composite membrane characterized in that it comprises an electron insulating proton conductor of the system. 4 4 443 4 4 4 4 • 4 4 4444 4 4 4 4 4 4 4 4 4 4 44 4 ** · 4 membrane electrodes capable of converting the chemical energy of a reaction into electrical energy at a temperature of about X ° C to about Y ° C, where Y is greater than X, wherein X and Y are selected from the group consisting of 175, 180 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430 , 440, 450, 460, 470, 480, 490, 500, 510, 520, 530 and 540, wherein the electronically insulated proton conductor contains no acid to maintain conductivity. 48. A membrane electrode assembly comprising an electronically insulating proton conductor and which is capable of converting a chemical reaction energy into electrical energy at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X and Y are selected. from the group comprising 220,230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 410, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520 530 and 540. 49. A membrane electrode assembly comprising an electronically insulating proton conductor and capable of converting a chemical reaction energy into electrical energy at a temperature of about X ° C to about Y ® C, wherein Y is greater than X, wherein X and Y are are selected from groups containing 175 180 190, 200, 210, 220, 230, 240, 250 260, 270 280, 290 300, 310 320, 330, 340, 350, 360, 370 380 390, 400 410, 420 430, 440 450, 460, 470, 480, 490, 500, 510, 520, 530 and 540, wherein the electronically insulated proton conductor contains no acid to maintain conductivity. 50. A fuel cell comprising an electronically insulated proton conductor, wherein the fuel cell is capable of converting a chemical reaction energy into electrical energy. 9 999 At a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X a 4 9 9 9 9 9999994 9 44 4 44 Y are selected that groups containing 220,230 240, 250 260, 270, 280, 290, 300 310 , 320, 330, 340, 350 370 380 390, 400, 410, 410, 420 430 , 440, 450, 460, 470, 480 490 500 510, 520, 530 and 540. 51. A fuel cell comprising an electronically insulated proton conductor, wherein the fuel cell is capable of converting chemical energy into electrical energy at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X and Y are selected 2e groups 175, 180, 190, 200 210, 220, 230, 240, 250, 260, 270, 280, 290 300, 310, 320, 330 340, 350, 360, 370, 380, 390, 400, 410, 420 430, 440, 450, 460 470, 480, 490, 500, 510, 520, 530 and 540 taking electronically insulating the proton conductor contains no acid to maintain conductivity. 52. A fuel cell comprising electrodes and means susceptible to exposure to at least one chemical for converting a chemical energy reaction into electrical energy at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X is and Y are selected from the group containing 220,230, 240, 250, 260, 270, 280, 290, 300 310, 320 330, 350, 350 360, 370, 380, 390, 400, w. 410, 410, 420 430, 440 450, 460, 470 480, 490, 500, 510, 520, il 530 and 540. 53. Fuel article, marked ý t í m, in that contain e electrodes and means susceptible to exposure to at least one chemical, for converting the chemical energy response into electrical energy at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X and Y is selected from the group consisting of 175, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, *; **; · 4 ··· ···· ·. .4 ·· · · * * · 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530 and 540, the electron insulating proton conductor containing no acid to preserve conductivity. 54. An electricity generating system comprising a fuel reformer and a fuel cell, wherein the fuel cell is capable of converting chemical reaction energy into electrical energy at a temperature of about X ° C to about Y ° C, where Y is greater than X, wherein X and Y are selected from the group containing 220, 230, 240, 250, 260, 270 280, 290, 300, 310, 320 330 340 350, 360, 370, 380, 390, 400 410, 410, 420, 430, 440 450 460 470, 480, 490, 500, 510, 520 530 a 540. 55. System for creating electricity, y znače n ý team that comprising a fuel reformer and a fuel cell, wherein the fuel cell is capable of converting a chemical energy reaction into electrical energy at a temperature of about X ° C to about Y ° C, where Y is greater than X, wherein X and Y are selected from groups containing 175, 180, 190, 200, 210, 220 230, 240, 250 260, 270, 280, 290 300, 310, 320, 330, 350, 350 360, 370 380 390, 400, 410, 420 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530 and 540, wherein the electronically insulated proton conductor contains no acid to maintain conductivity. 56. A method for converting a chemical energy reaction into electrical energy, comprising exposing an electronically insulating proton conductor to a chemical at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X and Y are selected from Groups containing 220,230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, tttt * • ··· ♦ • tttttt • tt • «• tt 410, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520 530 and 540. ♦ tt tt tttt 57. A method for converting a chemical energy reaction into electrical energy, comprising subjecting the electronically insulating proton conductor to a chemical at a temperature of about X ° C to about Y ° C, wherein Y is greater than X, wherein X and Y are are selected from groups containing 175 180 190, 200, 210, 220, 230, 240, 250 260, 270, 280, 290 300, 310 320, 330, 340, 350, 360, 370 380 390, 400, 410, 420 430, 440 450, 460, 470, 480, 490, 500, 510 520, 530 and 540 whereas electronically insulating the proton conductor contains none acid to se preserved conductivity. 58. The membrane electrode assembly of claim 5, 6, or 7 having a specific surface resistance in the range of about 0.01 to about 100 ohm.cm ² . 59. The fuel cell of claim 9 or 14, wherein the membrane electrode assembly has a specific surface resistance in the range of about 0.01 to 100 ohm.cm ² . 60. The fuel cell of claim 9, wherein the membrane electrode assembly has a specific material resistance having a thickness of about 175 microns and a proton conductivity within the gap of FIG. 1. 61. The fuel cell of claim 14, wherein the membrane electrode assembly has a specific material resistance having a thickness of about 175 microns and a proton conductivity within the gap of FIG. 2. • 4 v that 62. The system of claim 20, wherein the synthetic gas generator is capable of generating hydrogen.