The present invention generally relates to conducting ceramics for electrochemical systems and, in particular, to mixed ionically and electrically conducting ceramics.
Currently, there is great interest in using hydrogen as a fuel source. Hydrogen can be produced, for example, from carbonaceous fuels. Conventional methods for the separation of hydrogen from carbonaceous fuels typically require the steps as shown in
Syngas can be obtained by reacting a carbonaceous fuel with steam, air, or pure oxygen to create a mixture of hydrogen, carbon monoxide, carbon dioxide, water, and lower hydrocarbons. Particulates and contaminants produced by this reaction are removed in subsequent steps. The syngas stream is then reacted to form hydrogen gas through the water-gas shift reaction by passing the syngas stream over a suitable catalyst.
The water-gas shift reaction is as follows:
More advanced “shift” reactors attempt to attain chemical equilibria at a reduced temperature, while also performing the entire water-gas shift reaction in a single reactor. A subsequent separation step is thus required to remove the CO2 that is produced in this reaction, which in this process, is typically done by pressure swing adsorption techniques. However, pressure swing adsorption techniques can be energy intensive and cannot be performed in a continuous manner.
Other examples of methods of gas separation include diffusion methods that use a difference in diffusion coefficients between gas molecules passing through a material to effect gas separation. The materials used in these methods typically have either a microporosity that allows smaller molecules to diffuse at a higher rate than larger molecules, and/or preferentially dissolves certain atoms or molecules, which creates a difference in their ability to be transported through the material. However, fouling of these materials, as well as cost and energy intensity, are among the reasons that more advanced hydrogen gas separation methods are still needed.
In one aspect, the present invention generally relates to mixed ionically and electrically conducting materials in a variety of arrangements for a variety of uses. In one set of embodiments, the invention relates to conducting ceramics for electrochemical systems and, in particular, to mixed ionically and electrically conducting ceramics. Various embodiments of the invention involve relatively non-porous, or dense, mixed conducting materials, mixed conducting materials with relatively low combined resistivity, specific materials for use as mixed ionically and electrically conducting materials with particular phase particle or grain size or scale, and structures including mixed ionically and electrically conductive materials in multi-layer arrangements including porous and non-porous structures, some structures of which can support others in the arrangement.
The invention also relates, in another aspect, to systems for generating energy from a fuel in which a reactor allows fuel (and related impurities, if present) to be physically separated from a fuel cell or a related electrochemical energy conversion device that could be harmed or fouled by the impurities or other components of the fuel. The invention also relates, in certain embodiments, to electrochemical energy conversion systems able to react hydrogen to produce electrical energy and water, generating hydrogen from the water, and using the hydrogen as fuel in an electrochemical reaction to generate energy.
In yet another aspect, a system is provided which combines several of the individual invention aspects described herein. In this system, a fuel, including or based solely on hydrogen, is reacted in a first portion of the reactor (e.g., a fuel cell or other electrochemical device) to produce electrical energy. Exhaust, including water, is produced in the reaction, which is re-converted to hydrogen in a second portion of the reactor in an electrochemical reaction driven by consumption of a second, different fuel. The first portion and second portion may be contained within the same chamber or vessel, or the first and second portions may be in separate vessels that are in fluidic communication, e.g., using pipes, tubing, or the like.
The hydrogen thus generated can be used to generate electricity in the first portion, again producing water, which can be reconverted to hydrogen in the second portion in a cyclical manner, in some embodiments of the invention. In other embodiments, the hydrogen produced in the second portion from water produced by the first portion can also be used for other purposes, for example, as fuel for an electrochemical device not involving either the first or second portions.
In some embodiments, the second portion involves a mixed ionically and electrically conducting material which physically isolates the water produced in the first portion from a second fuel provided in the second portion, except for ionic and/or electronic conduction across the mixed conducting material. In this way, the second fuel, including any impurities if present, can be physically isolated from the first portion, thereby preventing contamination of the first portion if such contamination could be detrimental to the first portion.
The subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
In one aspect, the invention is a method. In one set of embodiments, the method includes acts of reacting a fuel comprising hydrogen to generate electricity and water in a first portion of a reactor, reacting the water to generate hydrogen in a second portion of the reactor, and reacting at least a portion of the hydrogen generated in the second portion of the reactor to produce electricity. The method, according to another set of embodiments, includes acts of reacting a fuel and water across a mixed ionically and electrically conducting material, wherein the water is isolated from the fuel except for ionic and electronic conduction across the material, to generate hydrogen, and reacting at least a portion of the hydrogen to produce electricity.
The method, in one set of embodiments, includes an act of reacting water to produce H2 having a purity of at least about 90% (not inclusive of any residual, unreacted water that may be present) using electrons provided by a material comprising a first phase comprising a ceramic ionic conductor and a second phase comprising a ceramic electrical conductor. In another set of embodiments, the method includes acts of reacting a carbonaceous fuel to produce electrons within a material, and reacting the electrons with water to produce oxygen ions within the material, the oxygen ions being able to react with the carbonaceous fuel. In yet another set of embodiments, the method includes acts of reacting an oxidizable species to produce electrons within a material, and reacting the electrons with a reducible species that is not in physical contact with the oxidizable species to produce H2. In some of these embodiments, the first phase is substantially interconnected throughout the material such that the material is ionically conductive, and the second phase is substantially interconnected throughout the material such that the material is electronically conductive.
In one set of embodiments, the method includes acts of providing a mixed ionically and electrically conducting material having a first side and a second side, flowing an oxidizable species across the first side of the material, and flowing a reducible species across the second side of the material in a direction that is substantially countercurrent relative to the flow of the oxidizable species.
The invention includes a reactor in another aspect. In one set of embodiments, the reactor includes a material separating a chamber into a first compartment and a second compartment, a carbonaceous fuel source in fluidic communication with an inlet of the first compartment, and a source of water in fluidic communication with an inlet of the second compartment. In certain embodiments, the material comprises a first phase comprising a ceramic ionic conductor and a second phase comprising a ceramic electrical conductor. In some cases, the first phase is substantially interconnected throughout the material such that the material is ionically conductive, and the second phase is substantially interconnected throughout the material such that the material is electronically conductive.
In another set of embodiments, the reactor comprises a mixed ionically and electrically conducting material having a first side and a second side, a source of an oxidizable species directed for flow across the first side of the material, and a source of a reducible species directed for flow across the second side of the material in a direction that is substantially countercurrent relative to the flow of the oxidizable species. The reactor, in yet another set of embodiments, includes a mixed ionically and electrically conducting material, having a porosity of less than about 1 open pore/mm2, separating a chamber into a first compartment and a second compartment.
In still another set of embodiments, the reactor includes a material separating a chamber into a first compartment and a second compartment, where the material comprises a first phase comprising a ceramic ionic conductor and a second phase comprising a ceramic electrical conductor. In some cases, the first phase is substantially interconnected throughout the material such that the material is ionically conductive, and the second phase is substantially interconnected throughout the material such that the material is electronically conductive. In certain embodiments, the ceramic electrical conductor includes a ceramic having a formula A1−xSrxTiO3, where x is between about 0.1 and about 0.5, and A represents one or more atoms, each independently selected from the group consisting of Y, La, Nb, Yb, Gd, Sm, and Pr.
The reactor, in another set of embodiments, comprises a mixed ionically and electrically conducting material separating a chamber into a first compartment and a second compartment. In some embodiments, the material comprises a first phase comprising a YSZ (“yttria-stabilized zirconia”) material and a second phase comprising a YST (“yttrium doped SrTiO3”) material. In some cases, the first phase is substantially interconnected throughout the material such that the material is ionically conductive, and the second phase is substantially interconnected throughout the material such that the material is electronically conductive. In still another set of embodiments, the reactor comprises a material separating a chamber into a first compartment and a second compartment, where the material has a resistivity of less than about 1000 Ohm cm. In some embodiments, the material comprises a first phase comprising a ceramic ionic conductor and a second phase comprising a ceramic electrical conductor. In still another set of embodiments, the reactor comprises a material separating a chamber into a first compartment and a second compartment.
Another aspect of the invention is directed to a system. The system includes, in one set of embodiments, a gasification chamber; a source of fuel in fluidic communication with the gasification chamber; a separation chamber, contained within the gasification chamber, fluidically separated from the gasification chamber, at least in part, by a material comprising a ceramic, wherein the material is ionically conductive; and a source of water in fluidic communication with the second compartment.
Yet another aspect of the invention is directed to an article. The article comprises, in one set of embodiments, a substantially non-porous material comprising a first phase comprising a ceramic ionic conductor and a second phase comprising a ceramic electrical conductor, and a porous substrate in physical contact with the material. In some cases, the first phase is substantially interconnected throughout the material such that the material is ionically conductive, and the second phase is substantially interconnected throughout the material such that the material is electronically conductive. In another set of embodiments, the article includes a first, porous mixed ionically and electrically conducting material, and a non-porous mixed ionically and electrically conducting material in physical contact with the first, porous mixed conduction material.
In another aspect, the present invention is directed to a method of making one or more of the embodiments described herein, for example, a material comprising a first phase comprising a ceramic ionic conductor, and a second phase comprising a ceramic electrical conductor. In yet another aspect, the present invention is directed to a method of using one or more of the embodiments described herein, for example, a material comprising a first phase comprising a ceramic ionic conductor, and a second phase comprising a ceramic electrical conductor.
Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the invention when considered in conjunction with the accompanying figures. In cases where the present specification and a document incorporated by reference include conflicting and/or inconsistent disclosure, the present specification shall control. If two or more documents incorporated by reference include conflicting and/or inconsistent disclosure with respect to each other, then the document having the later effective date shall control.
Non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention. In the figures:
The present invention generally relates, in some aspects, to conducting materials such as mixed ionically and electrically conducting materials. A variety of materials, material compositions, materials with advantageous ratios of ionically and electrically conducting components, structures including such materials, and the like are provided in accordance with the invention.
In one set of embodiments, the invention relates generally to conducting ceramics for electrochemical systems and, in particular, to mixed ionically and electrically conducting ceramics which can be used, for example, for hydrogen gas generation from a gasified hydrocarbon stream. While mixed ceramic conductors are known in the art, the present invention provides, in various embodiments, multi-phase systems of select materials combined in specific ways to achieve advantageous conductive properties, thin conductive materials optionally supported in multi-layer arrangements, and the like.
One aspect of the invention provides a material comprising a first phase comprising a ceramic ionic conductor, and a second phase comprising a ceramic electrical conductor. An example of such a material is a material comprising ZrO2 doped with Sc2O3 and yttrium-doped SrTiO3. Another aspect of the invention provides systems and methods of hydrogen gas generation from a fuel, such as a carbonaceous fuel, using materials such as those described above, for example, present within a membrane in a reactor. In some embodiments, a substantially pure hydrogen stream may be generated through in situ electrolysis. In some cases, a material such as those described above may be used to facilitate ion and/or electron exchange between a first reaction involving a fuel such as a carbonaceous fuel, and a second reaction involving a water-hydrogen conversion reaction (i.e., where water is reduced to produce hydrogen gas). In other aspects, the invention provides systems and methods for producing power from a fuel source, such as a carbonaceous fuel source.
Various embodiments of the invention use fuels such as carbonaceous fuels for consumption and/or driving various chemical reactions such as the production of hydrogen. Examples of carbonaceous fuels include, but are not limited to, conductive carbon, graphite, quasi-graphite, coal, coke, charcoal, fullerene, buckminsterfullerene, carbon black, activated carbon, decolorizing carbon, hydrocarbon fuels, an oxygen-containing hydrocarbon, carbon monoxide, fats, oils, a wood product, a biomass and combinations thereof. Hydrocarbon fuels can be arbitrarily represented using the formula CxHy, although in reality, hydrocarbon fuels may also contain additional impurities besides carbon and hydrogen, for example, sulfur (S), oxygen (O), nitrogen (N), or the like. It should therefore be understood that, as used herein, references to “hydrocarbon fuels” or “CxHy” may also include other impurities besides pure hydrocarbons, such as sulfur, oxygen, nitrogen, etc. Thus, non-limiting examples of hydrocarbon fuels will include saturated and unsaturated hydrocarbons, aliphatics, alicyclics, aromatics, and mixtures thereof. Other non-limiting examples of hydrocarbon fuels include gasoline, diesel, kerosene, methane, propane, butane, natural gas, and mixtures thereof. Examples of oxygen-containing hydrocarbon fuels include alcohols which further include C1-C20 alcohols and combinations thereof. Specific examples include methanol, ethanol, propanol, butanol and mixtures thereof.
One embodiment of the invention uses, as a fuel, coal, such as bituminous coal. Natural coal contains significant amounts of bound hydrogen and water. For instance, in bituminous Kentucky coal, the atomic composition is approximately CH0.81O0.08, which upon gasification yields a gas mixture with a partial oxygen pressure of about 10−20 atm at 800° C. Additional examples of suitable fuels include, but are not limited to, fluidized fuels such as gasified coal, gasified petroleum coke, gasified oils, gasified waxes, gasified plastics, gasified waste streams, gasified biologically derived fuels such as wood, agricultural waste, sewage sludge, or landfill gas, sewage treatment plant digester gas, natural gas, methane, propane, butane, diesel, gasoline, crude oil, bunker (a by-product from the petrochemical industry), etc.
As mentioned above, one aspect of the invention is directed to a material that is able to conduct both ions and electrons, i.e., the material exhibits “mixed conduction,” since the material is both ionically and electronically conducting. This material may be referred to herein as a “mixed ionically and electrically conducting material,” a “mixed conduction material,” or a “MIEC” material. For example, the material may include a unitary material that is both ionically and electronically conducting, or the material may comprise two or more discrete phases (i.e., discrete regions within the material that have substantially the same composition). For example, as is shown in
Different phases in a mixed conduction material can be identified, for example, by identification of the individual portions of material defining the ionically or electrically conductive portions. For example, where the mixed conduction material is ceramic, as described in more detail below, different phases can be identified by identification of individual ceramic grains within the material, in which each phase of the material generally comprises grains having different chemical compositions and/or lattice structures. Discrete phases within a material can be readily identified by those of ordinary skill in the art, for example, using known techniques such as electron microscopy or the like.
In some cases, the materials of the invention, or at least a portion of the material (for example, one or more discrete phases of the material), comprises a ceramic. For instance, in certain embodiments, the material comprises at least two phases, including a first phase comprising a ionic conductor, and a second phase comprising a electrical conductor, where the first phase and/or the second phase is a ceramic. Non-limiting examples of such materials include YST-YSZ compounds, YST-ScSZ compounds, YST-CGO compounds, or the like, as described in more detail below.
If two or more phases are present, in certain embodiments, they are arranged with respect to each other such that the first phase is substantially interconnected throughout the bulk of the material such that the material is ionically conductive, and/or the second phase is substantially interconnected throughout the material such that the material is electronically conductive. As used herein, “substantially interconnected” refers to a pathway that extends from a first surface of the material to a second surface that stays within only one phase of the material. Thus, for instance, an ionically conductive pathway would allow an ion, such as oxygen, to be transported from a first surface of the material to a second surface of the material while remaining in only one phase of the material, while an electronically conductive pathway would allow electrons to be transported within only one phase of the material from a first surface of the material to a second surface of the material. Preferably, multiple interconnected pathways exist in the material such that there are multiple ionically conductive pathways and multiple electrically conductive pathways from the first surface to the second surface of the material sufficient to achieve, in some embodiments, conductive and/or resistive properties as described below. Those of ordinary skill in the art can readily formulate materials using the disclosure herein to achieve these results. As examples, the material may comprise a first ionically conductive phase and a second electronically conductive phase that intertwines (e.g., 3-dimensionally) with the first phase, or the material may comprise a third phase, through which a first ionically conductive phase and a second electronically conductive phase pass.
If two phases are present in the material, the phases may be present in any ratio, for example, the ionically conductive phase may be present in the material at a percentage of between about 5% and 98% by weight, between about 10% and about 95% by weight, between about 30% and about 92% by weight, between about 40% and about 90% by weight, etc., with the balance being the electrically conductive phase. In some embodiments, for example in the case of ceramic mixed ionically and electrically conducting materials, one phase (e.g., the ionically conductive phase in the case of most ceramic materials) is significantly more resistive than the electrically conductive phase. The present invention recognizes this characteristic and, accordingly, provides the ability to tailor the ratios of the two materials relative to each other (as well as other properties such as density) to impart balanced conductivity while maintaining good conductivity of each phase throughout the material. That is, in such a situation more ionically conductive material can be provided relative to the electrically conductive material, to offset the increased resistivity of the ionically conductive phase, without altering the ratio of ionically to electrically conductive material so much so that the electrically conductive material is not present in sufficient quantity to provide sufficient electrically conductive interconnected pathways throughout the material to provide sufficient electric conductivity. For example, the ionically conductive phase may be present in a percentage as described above, or between about 50% to about 90% by weight, or 60% to about 88% by weight, with the balance being the electrically conductive phase. In other embodiments, these ratios exist between the ionically and electrically conductive phases relative to each other, but other components in the material can be present, reducing the overall amount of both the electrically and ionically conductive materials below their percentage presence relative to each other.
As used herein, a “ionically conducting material” is a material in which one or more types of ions are able to be transported through, for example, oxygen ions or hydrogen ions. In one set of embodiments, the ionic conductor is, or comprises, a ceramic ionic conductor. The ceramic ionic conductor may comprise, in some cases, one or more of a La-ferrite material, a ceria, and a zirconia, each of which may be doped or undoped, as described in more detail below. A non-limiting example of a ceramic ionic conductor is La-ferrite material, e.g., a material comprising La, Sr, Cr, Fe, and O (for example, an “LSCrF” material such as La0.2Sr0.8Cr0.2Fe0.8O3).
In some cases, the ceramic ionic conductor has a perovskite structure, or a cubic structure. At relatively low oxygen partial pressures (for example, at a pO2 below about 10−15 atm), the ceramic ionic conductor may have an ionic conductivity of about 0.2 S/cm to about 0.8 S/cm at a temperature of between about 800° C. and about 1000° C. In other cases, the ionic conductivity may be at least about 0.2 S/cm, at least about 0.3 S/cm, at least about 0.4 S/cm, at least about 0.5 S/cm, at least about 0.6 S/cm, at least about 0.7 S/cm, at least about 0.8 S/cm, at least about 0.9 S/cm, or at least about 1.0 S/cm or more at such temperatures.
In one embodiment, the ionic conductor comprises a cerate (i.e., a cerium oxide), for example, ceria or CeO2. Examples of ceria-containing materials include, but are not limited to, a CeO2-based perovskite, such as Ce0.9Gd0.1O2 or Ce1−xGdxO2, where x is no more than about 0.5, or lanthanum-doped ceria, such as (CeO)1−n(LaO5)n where n is from about 0.01 to about 0.2. In some cases, the ceria may be doped with gadolinium. For example, during production, a gadolinium oxide and a cerium oxide may be mixed together to produce a “CGO” (gadolinium-doped cerium oxide). The CGO material may have a perovskite structure. The CGO material may include about 10% to about 20% gadolinium, or about 12% to about 18% gadolinium. In certain cases the CGO material may have a conductivity of between about 0.06 S/cm and about 0.24 S/cm at a temperature of between about 700° C. and about 900° C., at relatively low oxygen partial pressures (e.g., below about 10−15 atm), and/or in an oxidizing atmosphere. Below a partial pressure of about 10−15 atm, the CGO material may exhibit higher ionic conductivities. For instance at a partial pressure of 10−18 atm and a temperature of 900° C., the CGO material may have an ionic conductivity of over about 0.4 S/cm and an electronic conductivity of about 1.6 S/cm. CGO may also have the added benefit of acting as a catalyst for reduction. Such a reduction may effectively increase the interfacial area of the material.
In yet another embodiment of the invention, the ionic conductor comprises a zirconia (i.e., a zirconium oxide material). Examples of zirconia materials include, but are not limited to, (ZrO2)(ZrO2)(HfO2)0.02(Y2O3)0.08, (ZrO2)(Y2O3)0.08, (ZrO2)(HfO2)0.02(Y2O3)0.08, (ZrO2)(HfO2)0.02(Y2O3)0.05, (ZrO2)(HfO2)0.02(Y2O3)0.08(TiO2)0.10, (ZrO2)(HfO2)0.02(Y2O3)0.08(Al2O3)0.10, (ZrO2)(Y2O3)0.08(Fe2O3)0.05, (ZrO2)(Y2O3)0.08(CoO)0.05, (ZrO2)(Y2O3)0.08(ZnO)0.05, (ZrO2)(Y2O3)0.08(NiO)0.05, (ZrO2)(Y2O3)0.08(CuO)0.05, (ZrO2)(Y2O3)0.08(MnO)0.05 and ZrO2CaO. In some embodiments, the zirconia may be stabilized in a cubic structure using one or more dopants, for example, metals such as nickel, or transition metals such as Y or Sc, which can be added in a quantity sufficient to give the doped zirconia a cubic structure. For instance, during production of the zirconia, yttria (Y2O3) and/or scandia (Sc2O3) may be added as a dopant material to produce a yttria-stabilized zirconia material (“YSZ”), a scandia-stabilized zirconia material (“ScSZ”), or a zirconia stabilized with both yttria and scandia. As used herein, a material that “stablizes” zirconia is a material that has been added (doped) to the zirconia in a quantity sufficient to cause the zirconia to form a cubic structure. The yttria and/or scandia may be added in any suitable concentration, for example, at mole ratios of about 2 mol %, about 4 mol %, about 6 mol %, about 8 mol %, about 10 mol %, etc. As non-limiting examples, an “8YSZ” material (i.e., a YSZ material doped with 8 mol % yttria) can be prepared, which may have an ionic conductivity of between about 0.02 S/cm to about 0.1 S/cm at a temperature of between about 800° C. and about 1000° C.; or a “10ScSZ” material (i.e., a ScSZ doped with 10 mol % scandia) can be prepared, which may have an ionic conductivity of between about 0.1 S/cm and about 0.3 S/cm at a temperature of between about 800° C. and about 1000° C. YSZ that is not compounded with an ionically-conductive material may also be useful in certain embodiments.
In still other embodiments, the ionic conductor may comprise a material having a formula (ZrO2)(HfO2)a(TiO2)b(Al2O3)c(Y2O3)d(MxOy)e where a is from 0 to about 0.2, b is from 0 to about 0.5 c is from 0 to about 0.5, d is from 0 to about 0.5, x is greater than 0 and less than or equal to 2, y is greater than 0 and less than or equal to 3, e is from 0 to about 0.5, and M is selected from the group consisting of calcium, magnesium, manganese, iron, cobalt, nickel, copper, and zinc. Non-limiting examples include a LaGaO3-based perovskite oxide, such as La1−xAxGa1−yByO3 where A can be Sr or Ca, B can be Mg, Fe, Co and x is from about 0.1 to about 0.5 and y is from about 0.1 to about 0.5 (e.g. La0.9Sr0.1Ga0.8Mg0.2O3); a PrGaO3-based perovskite oxide electrolyte, such as Pr0.93Sr0.07Ga0.85Mg0.15O3 or Pr0.93Ca0.07Ga0.85Mg0.15O3; and a Ba2In2O5-based perovskite oxide electrolyte, such as Ba2(In1−xGax)2O5 or (Ba1−xLax)In2O5, where is x is from about 0.2 to about 0.5.
As used herein, an “electronic conducting material” is a material through which electrons can be readily transported. The electronic conductor may be, for example, a conducting material or a semiconducting material. The electronic conductor, in one set of embodiments, may be, or comprise, a ceramic electronic conductor. For instance, the ceramic electronic conductor may comprise one or more of a LST material, a YST material, a YLST material, and an LCC material. As used herein, “LCC” refers to any lanthanum-calcium-chromium oxide, i.e., the LCC material comprises La, Ca, Cr, and O, for example, La0.8Ca0.2CrO3. La0.8Ca0.2CrO3 can have, in some embodiments, an electronic conductivity of ranging between about 40 S/cm (e.g., in reducing atmospheres) to about 80 S/cm (e.g., in oxidizing atmospheres). In some cases, pressureless sintering to full density of the LCC at 1400° C. may be used.
In one embodiment, the ceramic electronic conductor comprises a YST (Y—Sr—Ti) material, i.e., a ceramic material comprising Y, Sr, Ti, and O, for example, Sr0.88Y0.08TiO3. In some cases, the YST material may have a formula Y1−xLaxTiO3, where x may be between about 0.1 and about 0.5, or between about 0.2 and about 0.4 in some cases. YST materials may also have reduced electrode polarization in some cases. In some embodiments, the YST material may be prepared by doping SrTiO3 with yttrium. Such a YST material may have a relatively high electronic conductivity at an elevated temperature, for example, an electronic conductivity of about 50 S/cm to about 80 S/cm at a temperature of 800° C. and an oxygen partial of between about 10−14 and about 10−19 atm. As a particular non-limiting example, a YST material was prepared and sintered at a temperature of 1400° C. X-ray diffraction (“XRD”) analysis of this material showed no evidence of reactions (
In another embodiment, the ceramic electronic conductor may comprise a material comprising a LST (La—Sr—Ti) material, i.e., a ceramic material comprising La, Sr, Ti, and O. Such materials can be produced, for instance, by doping SrTiO3 with a lanthanum oxide. The LST material may have a formula Sr1−xLaxTiO3 in some embodiments, where x may be between about 0.1 and about 0.5, or between about 0.2 and about 0.4 in some cases. For example, the lanthanum oxide may be added at a dopant at concentrations of between about 20 mol % La and about 40 mol %.
In yet another embodiment, the ceramic electronic conductor may be both an LST and a YST material (a “YLST” material), i.e., the ceramic material comprises Y, La, Sr, Ti, and O. The YLST material may have a formula (YzSr1−z)1−xLaxTiO3 where x may be between about 0.1 and about 0.5, or between about 0.2 and about 0.4 in some cases, and z may be any number between 0 and 1, for example, 0.25, 0.5, 0.75, etc. In still other embodiments, the material may comprise a strontium titanate doped with one or more of Y, La, Nb, Yb, Gd, Sm, and Pr. For example, in one embodiment, the material has a formula A1−xSrxTiO3, where A represents one or more atoms, each independently selected from the group consisting of Y, La, Nb, Yb, Gd, Sm, or Pr, and x may be between about 0.1 and about 0.5, or between about 0.2 and about 0.4 in some cases. For instance, A1−x in this structure may represent A1a
As noted above, the invention provides materials in which both the electrically and ionically conducting phases perform well, and this generally means provision of a good network of interconnected, continuous ionically and electrically conductive pathways, respectively, throughout the material. Ratios of phases relative to each other (where two-phase materials are provided) are described above in this regard. Another factor which those of ordinary skill in the art can adjust based on the present disclosure, to achieve good conductivity, is the density of the material, and/or the porosity. A more dense material will, in general, include more contact between individual portions of material phases (e.g., grains of ceramic), maximizing the presence of continuous conductive pathways of each. For example, in certain cases, the mixed ionically and electrically conducting material may have a density of at least about 80%. For example, the density of the material may be at least about 85%, at least about 90%, or at least about 95%, as measured on a volumetric basis. Those of ordinary skill in the art will know of suitable techniques for measuring the relative density of a material on a volumetric basis.
In some embodiments, the mixed ionically and electrically conducting material is substantially non-porous, i.e., the porosity of the material is less than about 1 open pore/mm2, and this can improve ionic and/or electrical conductivity. For example, the material may have a porosity of less than about 1 open pore/mm2 less than about 1 open pore/cm2 or the like. “Open pores” can be measured in a material by creating a pressure differential from one side of the material to the other side that is at least about 5 psi (34.5 kPa), coating the lower-pressure surface with a thin film of a liquid such as alcohol, and determining the number of bubbles that are created due to the pressure differential, where the presence of a stream of bubbles indicates the presence of an open pore. Another example method of determining porosity is a helium leak test, where a leak rate in the order of at most 0.01 cm3/min of helium per cm2 of cell area and per psi of pressure would be required (1 psi is about 6.9 kilopascals (kPa)).
Combinations of density, non-porosity, ratio of ionically to electrically conductive phase, and/or other adjustments can be made based on this disclosure to tailor combined conductivity of material, i.e., combined (ionic and electrical) resistivity. For example, the material may have a resistivity of less than about 1000 Ohm cm (Ω cm), less than about 750 Ohm cm, less than about 500 Ohm cm, less than about 250 Ohm cm, less than about 200 Ohm cm, less than about 150 Ohm cm, less than about 100 Ohm cm, etc.
The material may also be substantially gas impermeable in certain cases, i.e., the material can be used to maintain separation of a first gas in a first compartment of a chamber on one side of the material and a second gas in a second compartment on another side of the material (for example, with compartments being on each side of the material, as illustrated schematically in
In other embodiments, however, the material is porous, and allows at least some gas to be transported therethrough. In some cases, the material may be selectively permeable, that is, permeable to some but not other gases. For example, the material may be permeable to hydrogen gas, but impermeable to other gases. In one embodiment, the material is sufficiently porous that pressure differences between a first side and a second side of the material may be used to direct the transport of gas across the material, e.g., from a higher pressure to a lower pressure. In other embodiments, the material is gas impermeable at ambient pressure, but at higher pressures, the material may be permeable or selectively permeable to gases.
In one set of embodiments, the invention provides structures using mixed ionically and electrically conducting materials. For example, the mixed ionically and electrically conducting material can be positioned in contact with a substrate, such as a porous substrate. The porous substrate may have a porosity that is at least sufficient to allow access to the material by gases such as oxygen, hydrogen, and/or water vapor, while providing at least some mechanical stability of the material, for instance, if the mixed ionically and electrically conducting material is present as a thin layer, for example, having a thickness of less than about 50 micrometers, for instance, between about 10 and about 20 micrometers or between about 10 and about 40 micrometers. The material, at these or other thicknesses, also may have a particularly high overall aspect ratio, i.e., its thickness may be quite small relative to another dimension perpendicular to the thickness, or to two other dimensions each perpendicular to the thickness. Where aspect ratio is defined as the ratio of at least one dimension perpendicular to thickness, to the thickness itself, mixed conductive material of the invention having an aspect ratio of at least about 5:1, 10:1, 20:1, 50:1, or 100:1 may be provided, optionally with an adjacent, supporting substrate that can be porous (e.g. in a layered arrangement). The substrate may have any shape. For example, in one embodiment, the material is deposited on the outside of a substrate that is a porous tube. In another embodiment, the material is deposited on the surface of a planar porous substrate. The porous substrate may be any suitable porous material, for example, a ceramic, a polymer, or a metal.
Accordingly, in one set of embodiments, a mixed ionically and electrically conducting material, which can be ceramic, is provided having a first side and a second opposing side, one or both sides addressed by a porous, supporting layer. One or more of the porous, supporting layers can, itself, be a mixed ionically and electrically conducting material, or simply ionically conductive or or electrically conductive, and each can, in some cases, be supported by an auxiliary, porous, inert layer. In one such arrangement, a multi-layer structure exists, comprising a first, porous layer, and a second, ceramic, dense mixed conduction material. In another arrangement, the multi-layer structure comprises first, porous layer, a second, ceramic, dense mixed conduction material, and a third, porous layer. In yet another arrangement, the multi-layer structure comprises a first, porous layer, a second, porous mixed conduction material, a third, ceramic, dense mixed conduction material, and a fourth porous mixed conduction material. In another arrangement, a multi-layer structure exists, comprising a first, porous layer, a second, porous mixed conduction material, a third, ceramic, dense mixed conduction material, a fourth, porous mixed conduction material, and a fifth, porous layer.
In some cases, e.g., if the surface of the deposited material is too “smooth,” an additional layer of powder may be added to the surface of the mixed conducting material that has been deposited on the porous substrate. For example, the powder may be a powder of the mixed conducting material, which can be deposited on a surface of the mixed conducting material, or another type of powder. In one embodiment, the additional layer of powder is deposited using vacuum intrusion, which may also assist in reducing polarization of the powder in some cases.
In another aspect of the invention, hydrogen, for example substantially pure hydrogen gas, is produced using a reactor containing a mixed ionically and electrically conducting material, such as those described herein. For example, with reference to
Oxygen that is produced from the reduction of water to hydrogen gas (or other reduction reaction) is transported across material 10 from compartment 22 to compartment 21, where it can react with the fuel, while electrons that are generated from the oxidation of the fuel return across material 10 to participate in the reduction of water to hydrogen gas. The hydrogen gas produced in this reaction may be separated and isolated, and/or routed to devices that can consume hydrogen, for example, fuel cells as discussed in detail below. Thus, in certain embodiments, a reactor of the invention may oxidize a fuel and simultaneously produce hydrogen gas within the same reactor.
In some embodiments, the oxygen used to oxidize the fuel comes only from the mixed conducting material at steady state, although additional oxygen may be added for start-up, thermal balance requirements. In other embodiments, however, additional oxygen may be supplied even during steady state, for example, if more complete oxidation of the fuel is desired, if higher reaction temperatures are needed, etc.
The hydrogen gas produced by the reactor may exit the reactor in a first stream, while waste gases produced from the oxidation of the fuel may exit the reactor in a second stream, and/or be used in other operations within the reactor. The hydrogen gas that is produced by the reactor is thus substantially pure and free of contaminants (gaseous, particulate, etc., e.g., which may be present within the fuel), as the hydrogen gas is produced in a physically separate compartment than the compartment where the fuel has been oxidized. Such a physically separate arrangement may be advantageous, for example, in embodiments where impurities or other components of the fuel could harm or foul the reduction of water to hydrogen gas. Thus, a substantially pure hydrogen stream can be produced in some embodiments. For example, the substantially pure hydrogen stream may be at least about 90%, at least about 95%, at least about 97%, at least about 98%, or at least about 99% pure on a volumetric basis. In other embodiments, however, some water may be present within the hydrogen stream exiting the reactor (i.e., a “wet hydrogen” stream). Of course, in such cases, such a wet hydrogen stream may optionally be subsequently separated into water and hydrogen gas, before and/or after leaving the reactor, for example, using a condensation operation.
In some cases, the waste gases may be recycled within the reactor, for example, to facilitate gasification of a fuel, for instance, a carbonaceous fuel such as coal. Examples of recycling processes are illustrated in
In some embodiments of the invention, the same pressure is used on both sides of the mixed conducting material. However, in other embodiments of the invention, the pressures on the material are not necessarily the same. For example, in some cases, the pressure within the water-hydrogen reaction compartment may be greater, while in other embodiments, the reaction in this compartment may be less than the pressure in the fuel oxidation compartment. In certain cases, one or both pressures on the material may be ambient pressure. Even if the material is porous and/or at least partially selectively permeable, substantially pure hydrogen gas can still be produced, for example, if the pressure in the water-hydrogen reaction compartment is greater than the pressure in the fuel oxidation compartment such that gases from the fuel oxidation compartment are not able to cross the material due to the pressure difference.
The reactor, as described above, does not necessarily require a water-gas shift reaction that produces hydrogen gas directly from syngas, and therefore raw gasified carbonaceous fuel streams can be oxidized to produce hydrogen gas, in contrast to prior art systems where a fuel or syngas stream needs to be additionally processed to be free of contaminants such as H2S, which can poison catalysts in those prior art systems. In certain embodiments, the reactor can be placed within a gasifier compartment itself (i.e., the compartment in which a carbonaceous fuel is reacted to produce a gasified hydrocarbon, such as syngas), for instance, as is illustrated in the example shown in
It should be noted that the system, as described above, is by way of example only and is not intended to be limiting, and other reactions are also contemplated within the scope of the present invention. For example, any reduction reaction may be used within the reduction compartment, besides the reduction of water to hydrogen gas, that is able to produce ions that can be transported across the mixed conducting material, for example, a reduction reaction that produces oxygen ions, hydrogen ions, or the like. Similarly, other fuels can be used besides carbonaceous fuels within the oxidation chamber, which fuels may produce electrons when oxidized (partially or completely) that can be transported across the mixed conducting material.
Those skilled in the art will recognize that the above-described system will work for any process in which there is an oxidizable species on one side of a mixed conducting material, as disclosed herein, and a reducible species on the other side. Thus, as another example, CO2 can be reduced to CO on one side of the mixed conducting material, while methane (for instance, from natural gas) may be oxidized on the other side of the mixed conducting material, e.g., as follows:
4CO2+8e−→4CO+4O2− cathode
CH4+4O2−→CO2+2H2O+8e− anode
In one set of embodiments, the flow within the reactor of the oxidizable species (e.g., a fuel) and the reducible species (e.g., water) may be co-current, e.g., the flow of both species across the mixed conducting material occurs in substantially the same direction. In other embodiments, however, the flow may be counter-current (e.g., the flow of both species is in substantially opposite directions) or cross-current (e.g., the flow of both species is not co-current nor counter-current flow). Counter-current flow may give certain advantages, for example, greater efficiency, or better purity of the resultant streams after reaction, relative to co-current or cross-current flow. For instance, in counter-current flow, an oxidiziable species entering the reactor may be substantially oxidized upon leaving the reactor (e.g., by being in electronic/ionic communication with a substantially unreduced reducible species near the outlet for the oxidizable species), while a reducible species entering the reactor may be substantially reduced upon leaving the reactor (e.g., by being in electronic/ionic communication with a substantially unoxidized oxidizable species near the outlet of the reducible species).
One non-limiting example of such a reactor is shown in
Typically, the hydrocarbon stream will include impurities, unreacted fuel, and the like. In some cases, these may be present as particles within the stream. In some cases, these may be removed from the hydrocarbon stream using separation techniques known to those of ordinary skill in the art, for example, using filters, cyclones, centrifugal separators, impingement separators, or the like. For example, as is shown in
The hydrocarbon stream, upon leaving cyclone 55, flows through stream 61 to reaction chamber 60. Also entering reaction chamber 60 is stream 62. Stream 62 contains water, for example, which may be present as steam. Reaction chamber 60 contains a mixed conducting material which separates the reaction chamber into two (or more compartments), at least one of which is fed by stream 61 and at least one of which is separately fed by stream 62. Within reaction chamber 60, the hydrocarbon stream is oxidized, for example, completely to produce CO2, while the water is reduced to H2, e.g., using the reaction schematic illustrated in
In some embodiments, depending on the efficiency of reaction chamber 60, a scrubber and/or an absorbent bed (not shown) may be added to stream 63. Stream 63, upon exiting reaction chamber 60, is fed back to gasifier 53. This creates a recycling operation that may increase the overall efficiency of the system. In the example shown in
Another example of an embodiment of the invention is shown in
The hydrogen gas produced using techniques such as those described above may be separated from the reactor, e.g., for use in reactions or power generation, or in some aspects of the invention, the hydrogen gas may be oxidized to produce electrical power, for example, in a fuel cell. In some cases, the process of power generation may occur simultaneously with hydrogen gas production. Any suitable system that can react hydrogen gas to produce water and power may be used, for example, fuel cells. Non-limiting examples of fuel cells include solid oxide fuel cells, molten carbonate fuel cells, phosphoric acid fuel cells, polymer electrolyte fuel cells (e.g., using proton exchange membranes), alkaline fuel cells, or the like. Thus, in one embodiment, hydrogen is provided in a reactor (e.g., supplied externally as a fuel, and/or produced by the reactor), which is reacted in a first portion of a reactor to produce water, and then re-converted to hydrogen in a second portion of the reactor. The hydrogen may be re-cycled back to the first portion of the reactor, e.g., as is shown in
The hydrogen gas may be used to regenerate water in the fuel cell, optionally producing electric current in the process, which may be harnessed. The fuel cell may be separate from the reactor where hydrogen is produced from water, for example, contained within a compartment or a vessel that is physically separate from, but is in fluidic communication with, the compartment in which hydrogen is produced from water; or in some cases, the fuel cell may be an integral part of the reactor, i.e., in a compartment of the reactor, a mixture of hydrogen and water (which may be present as steam) is simultaneously exposed to a reaction in which hydrogen is produced from water (e.g., using a mixed ionically and electrically conducting material, as previously described), and a reaction in which water is produced from hydrogen (e.g., in a fuel cell). The fuel cell may react H2 to produce water (H2O) by reaction with hydroxide ions (OH−), oxygen ions (O2−), carbonate ions (CO32−), etc., which in the process, may release electrons that can be harnessed as power 35.
It should be noted that the net result of such a reaction system, as is shown in
In
In
Another non-limiting example is shown in
It should be noted that these figures are intended to be schematic representations of useful general reaction schemes, and have been simplified for clarity. The reactions shown in
The following documents are incorporated herein by reference: International Patent Application Serial No.: PCT/US2005/035714, filed Oct. 5, 2005, entitled “Conducting Ceramics for Electrochemical Systems,” by Rackey, et al.; U.S. Provisional Patent Application Ser. No. 60/616,475, filed Oct. 5, 2004, entitled “Conducting Ceramics for Hydrogen Generation,” by Rackey, et al.; and U.S. Provisional Patent Application Ser. No. 60/662,321, filed Mar. 16, 2005, entitled “Conducting Ceramics for Electrochemical Systems,” by Rackey, et al.
The following examples are intended to illustrate certain embodiments of the present invention, but do not exemplify the full scope of the invention.
In this example, the hydrogen yield from a ceramic that is used to separate an oxidizable species on one side and a reducible species on the other side (see
In such cases, an electrical current, I, according to Ohm's law, may be expected:
I=V/R.
The voltage V can be calculated from the ratio of partial oxygen pressures on either side of the membrane using the Nernst equation. The resistance, R, can be divided into at least the following components: (1) a polarization resistance on the cathode due to the charge transfer, Rc; (2) an ohmic resistance resulting from the ionic transport through the membrane, Ri; (3) a polarization resistance on the anode due to the charge transfer, Ra; and (4) an electronic resistance that short circuits the cell, Re:
R=Rc+Ri+Ra+Re
The electronic resistance, Re, can be made negligible relative to R, in some embodiments, by an appropriate choice of ionic and/or electronic materials. The ionic resistance can depend on the material used, and may form a substantial proportion of R. It can be minimized, for example, by reducing the thickness to the minimum that is practically and reliably achievable from a ceramic processing standpoint. The polarization resistances may depend on the surface characteristics. Strategies to minimize these include increasing the reaction contact area, e.g., by using fine powders with catalytic properties. As a specific example, in some cases, an area specific total resistance of 400 mΩ cm2 (milliohm-cm2) can be achieved. At a Nernst voltage of 200 mV, this resistance results, based on these calculations, in a current of 0.5 A/cm2, which translates into a yield of 3.5 ml H2/cm2/min (volume measured at 1013 mbar and 273.15 K).
As a specific, non-limiting example, an estimate for the thickness of a particular membrane can be determined as follows. For the ionic conductivity, it can be assumed that the conductivity of ZrO2 stabilized with 8 mol % Y2O3 (8YSZ) at 800° C. is 0.024 S/cm. The presence of an electronic phase may dilute the ionic phase in some instances, which may have a significant effect on the effective conductivity. For example, in some cases, the electronic phase may constitute 50% of the volume; this may reduce the effective ionic conductivity to 30% of the ionic conductivity of the undiluted material. In such a case, a membrane thickness of 30%×400 mΩ cm2×0.024 S/cm=32 microns would be required. Ceramic membranes of this thickness and below can reliably be made at acceptably low leak rates.
The polarization resistance may include the remainder of the total resistance. At high temperatures (e.g., about 1000° C.) the kinetics at the reaction interface may be fast enough to be without significant polarization, so that additional catalysts may not be required in some cases. In some cases, however, e.g., at lower temperatures (750° C. to 800° C.), a high surface area coating of the material on the base membrane may also be useful.
This example illustrates a reactor according to one embodiment of the invention. The reactor used in this example is schematically shown in
Going from stream 57 to stream 63, the gas passes through the separator and the magnitude of the CO flow reduces as much as the CO2 flow increases. The formation of CO2 might seem rather low in relation to the total flow that enters the separator. This, however, is a result of the fact that the sequence stream 57, stream 63, and stream 66 form a loop, from which only a small amount is taken away during each passage. The reactor in the loop may therefore be exposed to larger flows. Some benefits are that concentration gradients across reactors are reduced and mass transfer is improved. Recycling of anode gas in fuel cell systems is also an example where this takes place.
The reaction equations of the separator in this example indicate that for each CO molecule that is converted, an H2 molecule is produced. Therefore, the difference in hydrogen flow between the H2 line and the steam line is equal to the conversion of CO, in this case 4.1 mol/s.
The efficiency of the process in terms of the latent heats of the net hydrogen produced, relative to the carbon consumed is (see Table 2):
where ΔHc=−400 kJ/mol is the combustion heat of carbon, ΔHH2=−242 kJ/mol is the heat of combustion of hydrogen (latent heat of vaporization values at 20° C.). The free enthalpy flux ratio of the net produced hydrogen stream and the ingoing carbon stream is equal to (see Table 3):
where ΔGc=−395 kJ/mol is the free enthalpy change of the oxidation of carbon, and ΔGHH2=−228 kJ/mol is the free enthalpy change of the oxidation of hydrogen, both at 20° C.
The free enthalpy change is the theoretical maximum amount of work (mechanical, electrical) that can be obtained from a reaction, according to this example. Therefore the above quotient identifies how much of the resulting work potential is still available relative to the work potential before the gases entered the system.
Table 3 shows the partial oxygen pressures in the streams to and from the separator and the resulting voltages that drives the oxygen ions through the membrane for this example. On the cathode side, i.e. the hydrogen side, there is a pO2 gradient ranging from 4.3×10−15 bar to 4.0×10−18 bar, going from inlet to outlet. This is representing an upgrade of the hydrogen content from 1% to 25%. As can be seen from the voltages in Table 4, a strong driving force is available down to pO2=4×10−18 bar. Increasing the hydrogen content to 50% brings the pO2 down to 8.9×10−20, leaving substantially less driving force (only 65 mV). This would reduce the yield of the membrane reactor, but would also lessen the steam production requirement per unit volume of hydrogen produced.
The following example illustrates the production of a mixed ionically and electrically conducting ceramic for use in a reactor, according to one embodiment of the invention.
Initially, a support tube was extruded and dried. The support tube is formed from Ni-YSZ, although the extrusion dough may contain, besides the Ni-YSZ precursors, binders, pore-formers etc. The Ni-YSZ tube was extruded using standard extrusion techniques known to those of ordinary skill in the art. The tube had a wall thickness of 1 mm and a diameter (green) of 9 mm. The tube was allowed to dry and harden before next step.
Next, a caps were added to the tube. The caps were circles cut from a green Ni-YZY sheet, and glued onto ends of tubes to form caps using Ni-YSZ slurry in a solvent. The cap was then bisque fired in air for 2 hours at 1100° C. An inner functional layer was then applied, after the tube had cooled. The functional layer was prepared by dip-coating the ceramic in a solution comprising Ni-CGO. The inner functional layer could optionally be sintered. In this sintering process, the tube was fired in air for 2 hours at 1100° C.
YSZ/YST was applied to the tube as follows. The tube was dip-coated in a solution comprising 50% YSZ and 50% YST by sintered volume. The YSZ/YST was then fired in air for 5 hours at 1350° C.
An outer functional layer was then applied, after the tube had again cooled. The functional layer was prepared by dip-coating the ceramic in a solution comprising Ni-CGO. The outer functional layer could optionally be sintered. In this sintering process, the tube was fired in air for 2 hours at 1000° C. to 1200° C.
The YST was then reduced at high temperatures. This was performed by firing the tube in hydrogen for 2 hours at 1100° C.
While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the scope of the present invention.
All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”
The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
It should also be understood that, unless clearly indicated to the contrary, in any methods claimed herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited.
In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.
This application is continuation of International Patent Application Serial No.: PCT/US2005/035714, filed Oct. 5, 2005, entitled “Conducting Ceramics for Electrochemical Systems,” by Rackey, et al., which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/616,475, filed Oct. 5, 2004, entitled “Conducting Ceramics for Hydrogen Generation,” by Rackey, et al.; and of U.S. Provisional Patent Application Ser. No. 60/662,321, filed Mar. 16, 2005, entitled “Conducting Ceramics for Electrochemical Systems,” by Rackey, et al. Each of the above applications is incorporated herein by reference.
Number | Date | Country | |
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60616475 | Oct 2004 | US | |
60662321 | Mar 2005 | US |
Number | Date | Country | |
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Parent | PCT/US05/35714 | Oct 2005 | US |
Child | 11529747 | Sep 2006 | US |