US20170275770A1 - Electrode-supported tubular solid-oxide electrochemical cell - Google Patents
Electrode-supported tubular solid-oxide electrochemical cell Download PDFInfo
- Publication number
- US20170275770A1 US20170275770A1 US15/618,474 US201715618474A US2017275770A1 US 20170275770 A1 US20170275770 A1 US 20170275770A1 US 201715618474 A US201715618474 A US 201715618474A US 2017275770 A1 US2017275770 A1 US 2017275770A1
- Authority
- US
- United States
- Prior art keywords
- electrode
- electrolyte
- substance
- solid
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C25B11/035—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
-
- C25B9/08—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8864—Extrusion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/002—Shape, form of a fuel cell
- H01M8/004—Cylindrical, tubular or wound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present disclosure relates to solid state electrochemical cells, more particularly to electrode-supported tubular solid-oxide electrochemical cells for use in electrochemical synthesis of chemicals and methods of making such electrode supported tubular solid-oxide electrochemical cells.
- Electrochemical cells that incorporate ion conducting solid electrolytes have shown great promise for gaseous chemical synthesis applications. Electrochemical synthesis using such ion conducting solid electrolytes can produce high purity gases at higher reaction rates, with lower cost and without several of the chemical by-products and detrimental environmental impacts of traditional catalytic chemical synthesis processes.
- Hydrogen gas (H 2 ) is an important starting material for many industrial chemicals and also important as a primary fuel source in renewable energy production.
- a carbonaceous feed such as natural gas, coal, liquefied petroleum gas, or the like, as follows:
- This process typically requires high temperatures (such as 700-1000° C.) and, in practice, involves various additional steps, such as removing sulfur from the carbonaceous feed.
- Ammonia (NH 3 ) is one of the most highly produced inorganic chemicals in the world because of its many commercial uses, such as in fertilizers, explosives and polymers. Modern commercial production of ammonia typically utilizes some variation of the Haber-Bosch process.
- the Haber-Bosch process involves the reaction of gaseous nitrogen (N 2 ) and hydrogen (H 2 ) on an iron-based catalyst at high pressures (such as 150-300 bar) and high temperature (such as 400-500° C.), as follows:
- the nitrogen feed typically derives from atmospheric air but the hydrogen feed typically derives from catalytic steam reforming of a carbonaceous feed stock, discussed above.
- implementation of this process requires various other steps, such as separating and purifying the hydrogen before it can be used.
- hydrogen gas can be produced by direct electrolysis of steam (H 2 0) without requiring a carbonaceous feed source and the commensurate production of carbon dioxide.
- Ammonia may be electrochemically produced by directly reacting the hydrogen with nitrogen, eliminating the need for intermediate steps to separate and purify the hydrogen before use in the synthesis reaction.
- Electrochemical synthesis is typically carried out using an electrochemical cell that incorporate two electrodes (an anode and a cathode) and an electrolyte that separates the two electrodes.
- the two electrodes are connected via electronic circuitry to a power source, and the electrolyte typically is a material that conducts ionic species but not electrons nor non-ionized species, such as the initial chemical reactants and final chemical products.
- the electrolyte typically is a material that conducts ionic species but not electrons nor non-ionized species, such as the initial chemical reactants and final chemical products.
- a voltage is applied across the two electrodes, a reactant is dissociated and ionized at one electrode, and the ionized reactant species migrates through the electrolyte toward the opposite electrode, where it reacts (in some cases with a second reactant that is present at the opposite electrode) to form the desired reaction product.
- the materials and configuration of the electrodes and electrolyte are selected and optimized depending on the desired electrochemical
- electrochemical cells For electrochemical synthesis to be widely applicable and commercially viable, there exists a need for electrochemical cells that may be fabricated using a variety of materials and in various configurations, depending on the desired electrochemical synthesis reaction, in a cost-effective and scalable way. Moreover, it is desirable for the electrochemical cells to have the structural and chemical stability and durability to withstand the potentially severe temperatures, pressures and chemical environments in which they would operate.
- the present disclosure provides a tubular solid-oxide electrochemical cell that includes a first porous electrode configured in a tubular shape, an electrolyte disposed as a thin-layer on at least part of a surface of the first porous electrode, and a second porous electrode disposed on at least a part of a surface of the electrolyte.
- the first porous electrode includes a first mixed ionically/electronically conductive composite material of a solid-oxide electrolyte substance and a first electrochemically active metallic substance.
- the electrolyte includes the solid-oxide electrolyte substance.
- the second porous electrode includes a second mixed ionically/electronically conductive composite material of the same solid-oxide electrolyte substance and a second electrochemically active metallic substance.
- the present disclosure provides a solid tubular solid-oxide electrochemical cell made by extruding an electrode dough in a tubular shape to form a first electrode, wherein the electrode dough includes a solid-oxide electrolyte substance, a first electrochemically active metallic substance, a carbon-based pore forming substance, a binder and a solvent; sintering the extruded first electrode to cause the carbon-based pore forming substance to burn off and form pores in the first electrode; forming an electrolyte onto at least part of a surface of the sintered first electrode, wherein the electrolyte is a thin-layer of the solid-oxide electrolyte substance; and forming a second electrode onto at least part of a surface of the electrolyte, wherein the second electrode includes the solid-oxide electrolyte material and a second electrochemically active metallic substance.
- the present disclosure provides a process for manufacturing a tubular solid-oxide electrochemical cell, including the steps of forming an electrode dough that includes a solid-oxide electrolyte substance, a first electrochemically active metallic substance, a first carbon-based pore forming substance, a first binder and a first solvent; extruding the electrode dough in a tubular shape to form a first electrode; and sintering the extruded first electrode.
- An electrolyte slurry including the solid-oxide electrolyte substance and a second solvent is formed and coated onto at least a part of a surface of the sintered first electrode, and the electrolyte coating sintered.
- An electrode slurry including the solid-oxide electrolyte substance, a second electrochemically active metallic substance, a second carbon-based pore forming substance and a third solvent is formed and coated onto at least a part of a surface of the sintered electrolyte, and the electrode coating is sintered.
- FIGS. 1A, 1B and 1C depict a tubular solid-oxide electrochemical cell according to one embodiment of the present disclosure.
- FIG. 2 shows a flow chart illustrating one embodiment of a process for manufacturing a tubular solid-oxide electrochemical cell according to the present disclosure.
- the present disclosure provides for cost-effective production of electrochemical cells for use in electrochemical synthesis that may be customized and optimized depending on the desired electrochemical synthesis reaction.
- the electrochemical cells of the present disclosure have a tubular configuration and are made of solid-oxide ceramic materials.
- Tubular solid-oxide electrochemical cells according to the present disclosure may be stacked and arranged in various configurations, and have the mechanical and chemical stability and durability to be used in commercial scale electrochemical synthesis of various gases, such as hydrogen, ammonia, nitric oxide, syngas, and others.
- FIG. 1A shows an isometric view of one embodiment of a tubular solid-oxide electrochemical cell 100 according to the present disclosure.
- the electrochemical cell 100 is supported by a first electrode 110 configured in a tubular shape, upon which an electrolyte 120 and a second electrode 130 are disposed.
- the electrolyte 120 is disposed as a thin-layer on at least a portion of a surface of the first electrode 110
- the second electrode 130 disposed on at least a portion of a surface of the electrolyte 120 .
- FIG. 1B shows a cross-sectional isometric view through the midsection
- FIG. 1C shows an axial cross-sectional view through part of the midsection, of the tubular solid-oxide electrochemical cell 100 shown in FIG. 1A
- the first electrode 110 has an average thickness (T 1 ) that is greater than the combined average thickness (T 2 ) of the thin-layer of the electrolyte 120 and the average thickness (T 3 ) of the second electrode 130 taken together.
- the relatively thick first electrode provides mechanical support for the electrochemical cell and allows the electrolyte to be thinner, which helps reduce both ohmic losses and the amount of energy needed to transport ions through the electrolyte.
- the average thickness of the first (support) electrode (T 1 ) is in a range of about 5 mm to about 50 mm
- the average thickness of the electrolyte (T 2 ) is in a range of about 5 microns to about 100 microns
- the average thickness of the second electrode is (T 3 ) is in a range of about 5 microns to about 100 microns.
- FIGS. 1A-1C show an embodiment having the electrolyte 120 being disposed on an outer surface of the first (support) electrode 110 , and the second electrode 130 being disposed on an outer surface of the electrolyte 120
- the present disclosure includes embodiments where the electrolyte and second electrode being formed on at least a portion of an inner surface of the first electrode and the electrolyte, respectively, so that the first (support) electrode is the outermost layer of the electrochemical cell.
- the first (support) electrode may function as the anode and the second electrode as the cathode, or vice versa (i.e., the first (support) electrode may function as the cathode and the second electrode as the anode).
- the electrolyte used in the present electrochemical cells typically is made of a solid-oxide electrolyte substance, such as a perovskite, a fluorite, and others known in the art.
- the solid-oxide electrolyte substance preferably is designed to have high ionic conductivity, low electronic conductivity, and high density so as to prevent non-ionized gaseous reactants from mixing.
- Perovskite commonly refers to a class of metal oxide materials having a general formula ABO 3 , where A refers to a metal cation having a relatively large ionic radius and B refers to a metal cation having a relatively small ionic radius.
- A refers to a metal cation having a relatively large ionic radius
- B refers to a metal cation having a relatively small ionic radius.
- the crystal structure of perovskite materials is highly tolerant to vacancy formation and encompasses various different phases (such as Aurivilius phase and Ruddleson Popper phase), making perovskite materials well suited for use as ion conducting electrolytes.
- A may include, but is not limited to, monovalent metal cations (M 1+ , such as Na, K), divalent metal cations (M 2+ , such as Ca, Sr, Ba, Pb), trivalent metal cations (M 3+ , such as Fe, La, Gd, Y) and combinations thereof.
- B may include, but is not limited to, pentavalent metal cations (M 5+ , such as Nb, W), tetravalent metal cations (M 4+ , such as Ce, Zr, Ti), trivalent metal cations (M 3+ , such as Mn, Fe, Co, Ga, Al) and combinations thereof.
- Fluorite commonly refers to a class of materials having a face-centered cubic structure and includes metal oxides having a general formula MO 2 , where “M” may include, but is not limited to, divalent metal cations (M 2+ , such as Ca, Sr, Ba, Mg), trivalent metal cations (M 3+ , such as Sc, Y, Yb, Er, Tm, La, Gd, Dy, Sm, Al, Ga, In), tetravalent metal cations (M 4+ , such as Ce, Zr, Th, Hf, Bi) and combinations thereof.
- M 2+ divalent metal cations
- M 3+ such as Sc, Y, Yb, Er, Tm, La, Gd, Dy, Sm, Al, Ga, In
- M 4+ such as Ce, Zr, Th, Hf, Bi
- pyrochlores having a general formula A 2 B 2 O 7 or A 2-x A′ x B 2 O 6 , where A is a trivalent metal cation such as Gd, S
- the solid-oxide electrolyte substance is selected to be a proton (H + ) conducting material, or an oxygen ion (O 2 ⁇ ) conducting material.
- the specific composition of the solid-oxide electrolyte substance and whether it acts as a proton conductor or an oxygen ion conductor will also depend on the desired electrochemical synthesis reaction, as the combination of metal ions (e.g., A, A′, B, or M) may be manipulated to minimize the chemical reactivity of the electrolyte to the reactants and reaction conditions as well as optimize the conductivity of the desired ionic reactant species.
- the first and second electrodes used in the present electrochemical cells typically are made of a mixed ionically/electronically conductive composite material of the solid-oxide electrolyte substance and an electrochemically active substance. Moreover, the first and second electrodes preferably are porous and chemically stable in the highly reducing or oxidizing environment in which the electrochemical cells operate. In some embodiments, the first and second electrodes are made of the same mixed ionically/electronically conductive composite material; in other embodiments, the first electrode is made of a first mixed ionically/electronically conductive composite material and the second electrode is made of a second mixed ionically/electronically conductive composite materials that is different from the first mixed ionically/electronically conductive composite material.
- the electrolyte and the electrodes typically have different thermal characteristics so that, upon heating, the electrolyte and the electrodes expand at different rates causing one or more of the electrodes to crack and/or split away from the electrolyte. It has been found that, when the electrodes of the present electrochemical cells are made of a composite material that incorporates the same solid-oxide electrolyte substance used in the electrolyte, it is possible to match the coefficients of thermal expansion (CTEs) of the electrodes' materials sufficiently with the CTE of the electrolyte's materials so as to prevent the cracking and/or splitting observed upon heating of prior art electrochemical cells.
- CTEs coefficients of thermal expansion
- the mixed ionically/electronically conductive composite materials used for the electrodes typically have at least about 70% by weight of the solid-oxide electrolyte substance and preferably have a coefficient of thermal expansion within about ⁇ 10% of that of the solid-oxide electrolyte substance.
- the electrodes provide the reaction sites for the oxidation and reduction half-reactions that make up the desired electrochemical synthesis reaction. Accordingly, the first and second electrodes incorporate an electrochemically active substance, such as metal or metal oxide or semiconductor substance, that helps catalyze the desired half-reactions and also provides electronic conductivity to the electrodes.
- an electrochemically active substance such as metal or metal oxide or semiconductor substance
- the electrochemically active substance used will depend on the desired electrochemical synthesis reaction, and may include, but is not limited to, Sc, Ti, Zn, Sr, Y, Zr, Au, Bi, Pb, Co, Pt, Ru, Pd, Ni, Cu, Ag, W, Os, Rh, Ir, Cr, Fe, Mo, V, Re, Mn, Nb, Ta, and oxides, alloys and mixtures thereof.
- the electrodes preferably have a porosity and microstructure that allow the reactant gases to migrate throughout the electrode to come into contact with the electrochemically active metallic substance, and dissociate and/or react according to the desired electrochemical synthesis reaction.
- the porosity and microstructure of the electrodes are provided by incorporating a carbon-based pore forming substance which is burned out from the mixed ionically/electronically conductive composite material during the formation of the electrodes, as will be discussed further below.
- the carbon-based pore-forming substance may include, but is not limited to, graphite powder, starch, powdered and/or particulate organic polymers (e.g., polymethylmethacrylate, acrylic resin, polyvinylchloride, and the like.).
- the amount and type of carbon-based pore forming material may be adjusted to create an optimal porous microstructure for the electrodes, depending on the desired electrochemical synthesis reaction.
- FIG. 2 shows a flow chart 200 outlining one embodiment of a process for manufacturing a tubular solid-oxide electrochemical cell according to the present disclosure.
- the first electrode is formed in a tubular shape by extruding an electrode dough, and the extruded first electrode is sintered before an electrolyte is coated onto at least a portion of a surface of the first electrode.
- a second electrode is coated onto at least a portion of a surface of the electrolyte, and the completed electrochemical cell is heated to sinter the second electrode.
- the ingredients for the first electrode are combined at 205 and mixed and milled at 210 , typically using a solvent in order to adjust the particle size and particle size distribution of the ingredients. Any solvent known and used in the art for milling, such as water, may be used.
- the ingredients for the first electrode include at least a solid-oxide electrolyte substance, a first electrochemically active substance, and a carbon-based pore-forming substance. One or more of the other additives discussed below may also be combined, mixed and milled with these ingredients. After milling to an appropriate particle size and distribution, the mixture of ingredients is dried at 220 .
- the binder may be any known aqueous or non-aqueous binder, such as polyvinyl pyrollidone, polyvinyl alcohol, polyvinyl butyral, an acrylic (such as a polymethacrylate, and the like), a polyacrylamide, a polyethylene oxide, an alginate, a cellulose (such as methylcellulose, ethylcellulose, and the like), a starch, a gum, a styrene or a binder system, such as the DuramaxTM binders (available from The Dow Chemical Company), as well as combinations and mixtures thereof.
- aqueous or non-aqueous binder such as polyvinyl pyrollidone, polyvinyl alcohol, polyvinyl butyral, an acrylic (such as a polymethacrylate, and the like), a polyacrylamide, a polyethylene oxide, an alginate, a cellulose (such as methylcellulose, ethylcellulose, and the like), a starch,
- the solvent may be any solvent used in ceramic manufacturing, such as water, acetone, ethanol, isopropanol, methyethyl ketone, ⁇ -terpineol, and the like, as well as combinations and mixtures thereof.
- the selection of binder will depend on the other electrode ingredients and the solvent, as the binder typically imparts wet and dry strength to the electrode dough and the resulting electrode and must be compatible with the solvent.
- additives that are known and used in ceramics manufacturing also may be added at 225 (if not added previously) to impart a consistency and other properties that allow the electrode dough to be smoothly extruded.
- additives may include: a dispersant, such as polyacrylic acid, a phosphoric ester of an alcohol or phenol (e.g., available under the BeycostatTM mark), and the like; a polymer or polymerization system, such as acrylamide with a cross linker (e.g., bis-acrylamide), an initiator (e.g., ammonium persulfate), and a catalyst (e.g., tetramethylethylenediamine); a plasticizer, such as diotylphthalate and the like; a viscosity modifier; a flocculent; and a lubricant.
- the electrode dough typically has about 30% to about 70% volume of solid ingredients, with the remaining volume being solvent.
- the electrode dough is extruded through a die at 240 to form a first electrode in a tubular shape.
- the tubular first electrode may be made to any length and diameter, though typically is from about 5 cm to about 150 cm in length with an inner dimension from about 0.5 cm to about 5 cm.
- the extruded tubular first electrode generally has a circular cross-section, but other cross-sectional shapes (such as semicircular, oval, square, rectangular, triangular, trapezoidal, star, etc.) are possible and within the scope of this present disclosure.
- a non-circular cross-section may provide certain advantages, such as cell packing, heat dissipation and/or reactant flow through or along or around the cell.
- the extruded tubular first electrode is dried and sintered at 250 .
- the extruded tubular first electrode is typically placed horizontally onto a holder that will prevent the first electrode from bending.
- the extruded tubular first electrode may be dried at room temperature for up to 48 hours, and then sintered to burn off the additives from the extruded tubular electrode.
- Sintering may involve gradually heating the extruded tubular electrode, for example, at a rate between about 0.1° C./minute to about 10° C./minute, though more typically between about 1° C./minute to about 2° C./minute, to a set temperature between about 800° C. to about 1600° C. and holding at the set temperature for up to about 12 hours.
- sintering may involve gradually heating in a stepwise manner to one or more intermediate set temperatures and holding at each intermediate set temperature in order to burn off various different additives.
- the extruded tubular electrode is sintered and the carbon-based pore forming substance, in particular, burns off, pores are left behind in the electrode, so that the sintered first electrode is a solid porous cermet (ceramic-metal) composite material.
- An electrolyte is formed at 260 by, for example, spray coating, dip coating or otherwise layering an electrolyte slurry (formed at 255 ) as a thin-layer onto at least a part of a surface of the sintered first electrode.
- the electrolyte may be formed onto a part of an inner surface or an outer surface of the sintered first electrode.
- the electrolyte slurry may be formed by combining the solid-oxide electrolyte substance with a solvent (such as discussed previously) and optionally one or more other additives (such as binders, dispersants, polymers, etc.
- the electrolyte slurry typically has about 10% to about 30% volume of solid ingredients, with the remaining volume being solvent.
- the electrolyte is then dried and sintered at 270 to form a solid electrolyte layer.
- a second electrode is formed at 280 by, for example, spray coating, dip coating or otherwise layering an electrode slurry (formed at 275 ) onto at least a part of a surface of the sintered electrolyte.
- the electrode slurry may be formed by combining the solid-oxide electrolyte substance, a second electrochemically active substance, and a carbon-based pore forming substance with a solvent (such as discussed previously) and optionally one or more other additives (such as binders, dispersants, polymers, etc. as discussed previously) that are commonly used in ceramics manufacturing; mixing and milling; and then adding more solvent to form a slurry having a consistency to be coated or layered onto the electrolyte.
- the electrode slurry typically has about 10% to about 30% volume of solid ingredients, with the remaining volume being solvent.
- the second electrode is then dried and sintered at 290 , as discussed previously, to form a solid porous second electrode.
Abstract
Description
- A portion of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office patent files or records, but otherwise reserves all copyright rights whatsoever. The following notice applies to the software and data as described below and in the drawings that form a part of this document: Copyright Low Emission Resources Corporation, 2015, All Rights Reserved.
- The present disclosure relates to solid state electrochemical cells, more particularly to electrode-supported tubular solid-oxide electrochemical cells for use in electrochemical synthesis of chemicals and methods of making such electrode supported tubular solid-oxide electrochemical cells.
- Electrochemical cells that incorporate ion conducting solid electrolytes have shown great promise for gaseous chemical synthesis applications. Electrochemical synthesis using such ion conducting solid electrolytes can produce high purity gases at higher reaction rates, with lower cost and without several of the chemical by-products and detrimental environmental impacts of traditional catalytic chemical synthesis processes.
- For example, the traditional catalytic production of hydrogen gas (H2) and of ammonia (NH3), and the steps involved in their commercial scale implementation, are very energy intensive processes and produce massive amounts of carbon dioxide (CO2), a greenhouse gas widely acknowledged by the global scientific community as contributing to the warming of the earth's atmosphere and oceans.
- Hydrogen gas (H2) is an important starting material for many industrial chemicals and also important as a primary fuel source in renewable energy production. Currently, most industrial hydrogen gas production involves catalytic steam reforming of a carbonaceous feed, such as natural gas, coal, liquefied petroleum gas, or the like, as follows:
-
- This process typically requires high temperatures (such as 700-1000° C.) and, in practice, involves various additional steps, such as removing sulfur from the carbonaceous feed.
- Ammonia (NH3) is one of the most highly produced inorganic chemicals in the world because of its many commercial uses, such as in fertilizers, explosives and polymers. Modern commercial production of ammonia typically utilizes some variation of the Haber-Bosch process. The Haber-Bosch process involves the reaction of gaseous nitrogen (N2) and hydrogen (H2) on an iron-based catalyst at high pressures (such as 150-300 bar) and high temperature (such as 400-500° C.), as follows:
-
N2+3H2→2NH3 - In modern ammonia-producing plants, the nitrogen feed typically derives from atmospheric air but the hydrogen feed typically derives from catalytic steam reforming of a carbonaceous feed stock, discussed above. In practice, implementation of this process requires various other steps, such as separating and purifying the hydrogen before it can be used.
- Commercial scale production of industrially important chemicals, such as hydrogen and ammonia, may be achieved more efficiently and cost effectively by electrochemical synthesis than by the traditional catalytic processes such as those discussed above. For example, hydrogen gas can be produced by direct electrolysis of steam (H20) without requiring a carbonaceous feed source and the commensurate production of carbon dioxide. Ammonia may be electrochemically produced by directly reacting the hydrogen with nitrogen, eliminating the need for intermediate steps to separate and purify the hydrogen before use in the synthesis reaction.
- Electrochemical synthesis is typically carried out using an electrochemical cell that incorporate two electrodes (an anode and a cathode) and an electrolyte that separates the two electrodes. As used in electrochemical synthesis applications, the two electrodes are connected via electronic circuitry to a power source, and the electrolyte typically is a material that conducts ionic species but not electrons nor non-ionized species, such as the initial chemical reactants and final chemical products. When a voltage is applied across the two electrodes, a reactant is dissociated and ionized at one electrode, and the ionized reactant species migrates through the electrolyte toward the opposite electrode, where it reacts (in some cases with a second reactant that is present at the opposite electrode) to form the desired reaction product. The materials and configuration of the electrodes and electrolyte are selected and optimized depending on the desired electrochemical synthesis reaction.
- For electrochemical synthesis to be widely applicable and commercially viable, there exists a need for electrochemical cells that may be fabricated using a variety of materials and in various configurations, depending on the desired electrochemical synthesis reaction, in a cost-effective and scalable way. Moreover, it is desirable for the electrochemical cells to have the structural and chemical stability and durability to withstand the potentially severe temperatures, pressures and chemical environments in which they would operate.
- In one aspect, the present disclosure provides a tubular solid-oxide electrochemical cell that includes a first porous electrode configured in a tubular shape, an electrolyte disposed as a thin-layer on at least part of a surface of the first porous electrode, and a second porous electrode disposed on at least a part of a surface of the electrolyte. The first porous electrode includes a first mixed ionically/electronically conductive composite material of a solid-oxide electrolyte substance and a first electrochemically active metallic substance. The electrolyte includes the solid-oxide electrolyte substance. The second porous electrode includes a second mixed ionically/electronically conductive composite material of the same solid-oxide electrolyte substance and a second electrochemically active metallic substance.
- In another aspect, the present disclosure provides a solid tubular solid-oxide electrochemical cell made by extruding an electrode dough in a tubular shape to form a first electrode, wherein the electrode dough includes a solid-oxide electrolyte substance, a first electrochemically active metallic substance, a carbon-based pore forming substance, a binder and a solvent; sintering the extruded first electrode to cause the carbon-based pore forming substance to burn off and form pores in the first electrode; forming an electrolyte onto at least part of a surface of the sintered first electrode, wherein the electrolyte is a thin-layer of the solid-oxide electrolyte substance; and forming a second electrode onto at least part of a surface of the electrolyte, wherein the second electrode includes the solid-oxide electrolyte material and a second electrochemically active metallic substance.
- In still another aspect, the present disclosure provides a process for manufacturing a tubular solid-oxide electrochemical cell, including the steps of forming an electrode dough that includes a solid-oxide electrolyte substance, a first electrochemically active metallic substance, a first carbon-based pore forming substance, a first binder and a first solvent; extruding the electrode dough in a tubular shape to form a first electrode; and sintering the extruded first electrode. An electrolyte slurry including the solid-oxide electrolyte substance and a second solvent is formed and coated onto at least a part of a surface of the sintered first electrode, and the electrolyte coating sintered. An electrode slurry including the solid-oxide electrolyte substance, a second electrochemically active metallic substance, a second carbon-based pore forming substance and a third solvent is formed and coated onto at least a part of a surface of the sintered electrolyte, and the electrode coating is sintered.
- For a better understanding of the nature, objects, and processes involved in this disclosure, reference should be made to the detailed description taken in conjunction with the accompanying drawings, in which:
-
FIGS. 1A, 1B and 1C depict a tubular solid-oxide electrochemical cell according to one embodiment of the present disclosure; and -
FIG. 2 shows a flow chart illustrating one embodiment of a process for manufacturing a tubular solid-oxide electrochemical cell according to the present disclosure. - The present disclosure provides for cost-effective production of electrochemical cells for use in electrochemical synthesis that may be customized and optimized depending on the desired electrochemical synthesis reaction. The electrochemical cells of the present disclosure have a tubular configuration and are made of solid-oxide ceramic materials. Tubular solid-oxide electrochemical cells according to the present disclosure may be stacked and arranged in various configurations, and have the mechanical and chemical stability and durability to be used in commercial scale electrochemical synthesis of various gases, such as hydrogen, ammonia, nitric oxide, syngas, and others.
-
FIG. 1A shows an isometric view of one embodiment of a tubular solid-oxideelectrochemical cell 100 according to the present disclosure. Theelectrochemical cell 100 is supported by afirst electrode 110 configured in a tubular shape, upon which anelectrolyte 120 and asecond electrode 130 are disposed. As shown inFIG. 1A , theelectrolyte 120 is disposed as a thin-layer on at least a portion of a surface of thefirst electrode 110, and thesecond electrode 130 disposed on at least a portion of a surface of theelectrolyte 120. -
FIG. 1B shows a cross-sectional isometric view through the midsection, andFIG. 1C shows an axial cross-sectional view through part of the midsection, of the tubular solid-oxideelectrochemical cell 100 shown inFIG. 1A . Thefirst electrode 110 has an average thickness (T1) that is greater than the combined average thickness (T2) of the thin-layer of theelectrolyte 120 and the average thickness (T3) of thesecond electrode 130 taken together. The relatively thick first electrode provides mechanical support for the electrochemical cell and allows the electrolyte to be thinner, which helps reduce both ohmic losses and the amount of energy needed to transport ions through the electrolyte. Typically, the average thickness of the first (support) electrode (T1) is in a range of about 5 mm to about 50 mm, the average thickness of the electrolyte (T2) is in a range of about 5 microns to about 100 microns, and the average thickness of the second electrode is (T3) is in a range of about 5 microns to about 100 microns. - While
FIGS. 1A-1C show an embodiment having theelectrolyte 120 being disposed on an outer surface of the first (support)electrode 110, and thesecond electrode 130 being disposed on an outer surface of theelectrolyte 120, the present disclosure includes embodiments where the electrolyte and second electrode being formed on at least a portion of an inner surface of the first electrode and the electrolyte, respectively, so that the first (support) electrode is the outermost layer of the electrochemical cell. - Moreover, depending on the desired electrochemical synthesis reaction, the selection of the electrolyte and the configuration of the reaction apparatus, the first (support) electrode may function as the anode and the second electrode as the cathode, or vice versa (i.e., the first (support) electrode may function as the cathode and the second electrode as the anode).
- The electrolyte used in the present electrochemical cells typically is made of a solid-oxide electrolyte substance, such as a perovskite, a fluorite, and others known in the art. The solid-oxide electrolyte substance preferably is designed to have high ionic conductivity, low electronic conductivity, and high density so as to prevent non-ionized gaseous reactants from mixing.
- Perovskite commonly refers to a class of metal oxide materials having a general formula ABO3, where A refers to a metal cation having a relatively large ionic radius and B refers to a metal cation having a relatively small ionic radius. The crystal structure of perovskite materials is highly tolerant to vacancy formation and encompasses various different phases (such as Aurivilius phase and Ruddleson Popper phase), making perovskite materials well suited for use as ion conducting electrolytes. “A” may include, but is not limited to, monovalent metal cations (M1+, such as Na, K), divalent metal cations (M2+, such as Ca, Sr, Ba, Pb), trivalent metal cations (M3+, such as Fe, La, Gd, Y) and combinations thereof. “B” may include, but is not limited to, pentavalent metal cations (M5+, such as Nb, W), tetravalent metal cations (M4+, such as Ce, Zr, Ti), trivalent metal cations (M3+, such as Mn, Fe, Co, Ga, Al) and combinations thereof.
- Fluorite commonly refers to a class of materials having a face-centered cubic structure and includes metal oxides having a general formula MO2, where “M” may include, but is not limited to, divalent metal cations (M2+, such as Ca, Sr, Ba, Mg), trivalent metal cations (M3+, such as Sc, Y, Yb, Er, Tm, La, Gd, Dy, Sm, Al, Ga, In), tetravalent metal cations (M4+, such as Ce, Zr, Th, Hf, Bi) and combinations thereof.
- Other metal oxide materials that may be used for the solid-oxide electrolyte substance according to the present disclosure include pyrochlores (having a general formula A2B2O7 or A2-xA′xB2O6, where A is a trivalent metal cation such as Gd, Sm, La, Nd, Eu, Tb, Bi, Y, Dy; A′ is a divalent metal cation such as Ca; and B is a tetravalent metal cation such as Ti, Zr, Ru), brownmillerite (A2B2O5, where A is a divalent cation such as Al, Ca, Sr, Ba; and B is a trivalent metal cation such as Fe, In, Ga, Mn, Cr, Zr, Hf, Ce, Ti) and the like.
- Depending on the desired electrochemical synthesis reaction, the solid-oxide electrolyte substance is selected to be a proton (H+) conducting material, or an oxygen ion (O2−) conducting material. The specific composition of the solid-oxide electrolyte substance and whether it acts as a proton conductor or an oxygen ion conductor will also depend on the desired electrochemical synthesis reaction, as the combination of metal ions (e.g., A, A′, B, or M) may be manipulated to minimize the chemical reactivity of the electrolyte to the reactants and reaction conditions as well as optimize the conductivity of the desired ionic reactant species.
- The first and second electrodes used in the present electrochemical cells typically are made of a mixed ionically/electronically conductive composite material of the solid-oxide electrolyte substance and an electrochemically active substance. Moreover, the first and second electrodes preferably are porous and chemically stable in the highly reducing or oxidizing environment in which the electrochemical cells operate. In some embodiments, the first and second electrodes are made of the same mixed ionically/electronically conductive composite material; in other embodiments, the first electrode is made of a first mixed ionically/electronically conductive composite material and the second electrode is made of a second mixed ionically/electronically conductive composite materials that is different from the first mixed ionically/electronically conductive composite material.
- In prior art electrochemical cells, the electrolyte and the electrodes typically have different thermal characteristics so that, upon heating, the electrolyte and the electrodes expand at different rates causing one or more of the electrodes to crack and/or split away from the electrolyte. It has been found that, when the electrodes of the present electrochemical cells are made of a composite material that incorporates the same solid-oxide electrolyte substance used in the electrolyte, it is possible to match the coefficients of thermal expansion (CTEs) of the electrodes' materials sufficiently with the CTE of the electrolyte's materials so as to prevent the cracking and/or splitting observed upon heating of prior art electrochemical cells. The mixed ionically/electronically conductive composite materials used for the electrodes typically have at least about 70% by weight of the solid-oxide electrolyte substance and preferably have a coefficient of thermal expansion within about ±10% of that of the solid-oxide electrolyte substance.
- When the present electrochemical cells are used for electrochemical synthesis reactions, the electrodes provide the reaction sites for the oxidation and reduction half-reactions that make up the desired electrochemical synthesis reaction. Accordingly, the first and second electrodes incorporate an electrochemically active substance, such as metal or metal oxide or semiconductor substance, that helps catalyze the desired half-reactions and also provides electronic conductivity to the electrodes. The electrochemically active substance used will depend on the desired electrochemical synthesis reaction, and may include, but is not limited to, Sc, Ti, Zn, Sr, Y, Zr, Au, Bi, Pb, Co, Pt, Ru, Pd, Ni, Cu, Ag, W, Os, Rh, Ir, Cr, Fe, Mo, V, Re, Mn, Nb, Ta, and oxides, alloys and mixtures thereof.
- Additionally, the electrodes preferably have a porosity and microstructure that allow the reactant gases to migrate throughout the electrode to come into contact with the electrochemically active metallic substance, and dissociate and/or react according to the desired electrochemical synthesis reaction. The porosity and microstructure of the electrodes are provided by incorporating a carbon-based pore forming substance which is burned out from the mixed ionically/electronically conductive composite material during the formation of the electrodes, as will be discussed further below. The carbon-based pore-forming substance may include, but is not limited to, graphite powder, starch, powdered and/or particulate organic polymers (e.g., polymethylmethacrylate, acrylic resin, polyvinylchloride, and the like.). The amount and type of carbon-based pore forming material may be adjusted to create an optimal porous microstructure for the electrodes, depending on the desired electrochemical synthesis reaction.
-
FIG. 2 shows aflow chart 200 outlining one embodiment of a process for manufacturing a tubular solid-oxide electrochemical cell according to the present disclosure. In general, the first electrode is formed in a tubular shape by extruding an electrode dough, and the extruded first electrode is sintered before an electrolyte is coated onto at least a portion of a surface of the first electrode. After the electrolyte coated first electrode is sintered, a second electrode is coated onto at least a portion of a surface of the electrolyte, and the completed electrochemical cell is heated to sinter the second electrode. The steps involved in this embodiment will be discussed in more detail below. - The ingredients for the first electrode are combined at 205 and mixed and milled at 210, typically using a solvent in order to adjust the particle size and particle size distribution of the ingredients. Any solvent known and used in the art for milling, such as water, may be used. The ingredients for the first electrode include at least a solid-oxide electrolyte substance, a first electrochemically active substance, and a carbon-based pore-forming substance. One or more of the other additives discussed below may also be combined, mixed and milled with these ingredients. After milling to an appropriate particle size and distribution, the mixture of ingredients is dried at 220.
- A binder and solvent are added at 225 to the mixture of ingredients and the resulting combination mixed and aged at 230 to form an electrode dough. The binder may be any known aqueous or non-aqueous binder, such as polyvinyl pyrollidone, polyvinyl alcohol, polyvinyl butyral, an acrylic (such as a polymethacrylate, and the like), a polyacrylamide, a polyethylene oxide, an alginate, a cellulose (such as methylcellulose, ethylcellulose, and the like), a starch, a gum, a styrene or a binder system, such as the Duramax™ binders (available from The Dow Chemical Company), as well as combinations and mixtures thereof. The solvent may be any solvent used in ceramic manufacturing, such as water, acetone, ethanol, isopropanol, methyethyl ketone, α-terpineol, and the like, as well as combinations and mixtures thereof. The selection of binder will depend on the other electrode ingredients and the solvent, as the binder typically imparts wet and dry strength to the electrode dough and the resulting electrode and must be compatible with the solvent.
- One or more other additives that are known and used in ceramics manufacturing also may be added at 225 (if not added previously) to impart a consistency and other properties that allow the electrode dough to be smoothly extruded. Such additives may include: a dispersant, such as polyacrylic acid, a phosphoric ester of an alcohol or phenol (e.g., available under the Beycostat™ mark), and the like; a polymer or polymerization system, such as acrylamide with a cross linker (e.g., bis-acrylamide), an initiator (e.g., ammonium persulfate), and a catalyst (e.g., tetramethylethylenediamine); a plasticizer, such as diotylphthalate and the like; a viscosity modifier; a flocculent; and a lubricant. The electrode dough typically has about 30% to about 70% volume of solid ingredients, with the remaining volume being solvent.
- After aging, the electrode dough is extruded through a die at 240 to form a first electrode in a tubular shape. Any known extrusion method may be used. The tubular first electrode may be made to any length and diameter, though typically is from about 5 cm to about 150 cm in length with an inner dimension from about 0.5 cm to about 5 cm. The extruded tubular first electrode generally has a circular cross-section, but other cross-sectional shapes (such as semicircular, oval, square, rectangular, triangular, trapezoidal, star, etc.) are possible and within the scope of this present disclosure. For some implementations, depending on the particular synthesis reaction and reactor configuration, a non-circular cross-section may provide certain advantages, such as cell packing, heat dissipation and/or reactant flow through or along or around the cell.
- The extruded tubular first electrode is dried and sintered at 250. During drying and sintering, the extruded tubular first electrode is typically placed horizontally onto a holder that will prevent the first electrode from bending. The extruded tubular first electrode may be dried at room temperature for up to 48 hours, and then sintered to burn off the additives from the extruded tubular electrode. Sintering may involve gradually heating the extruded tubular electrode, for example, at a rate between about 0.1° C./minute to about 10° C./minute, though more typically between about 1° C./minute to about 2° C./minute, to a set temperature between about 800° C. to about 1600° C. and holding at the set temperature for up to about 12 hours. In some embodiments, sintering may involve gradually heating in a stepwise manner to one or more intermediate set temperatures and holding at each intermediate set temperature in order to burn off various different additives. As the extruded tubular electrode is sintered and the carbon-based pore forming substance, in particular, burns off, pores are left behind in the electrode, so that the sintered first electrode is a solid porous cermet (ceramic-metal) composite material.
- An electrolyte is formed at 260 by, for example, spray coating, dip coating or otherwise layering an electrolyte slurry (formed at 255) as a thin-layer onto at least a part of a surface of the sintered first electrode. The electrolyte may be formed onto a part of an inner surface or an outer surface of the sintered first electrode. The electrolyte slurry may be formed by combining the solid-oxide electrolyte substance with a solvent (such as discussed previously) and optionally one or more other additives (such as binders, dispersants, polymers, etc. as discussed previously) that are commonly used in ceramics manufacturing; mixing and milling; and then adding more solvent to form a slurry having a consistency to be coated or layered onto the first electrode. The electrolyte slurry typically has about 10% to about 30% volume of solid ingredients, with the remaining volume being solvent. The electrolyte is then dried and sintered at 270 to form a solid electrolyte layer.
- A second electrode is formed at 280 by, for example, spray coating, dip coating or otherwise layering an electrode slurry (formed at 275) onto at least a part of a surface of the sintered electrolyte. The electrode slurry may be formed by combining the solid-oxide electrolyte substance, a second electrochemically active substance, and a carbon-based pore forming substance with a solvent (such as discussed previously) and optionally one or more other additives (such as binders, dispersants, polymers, etc. as discussed previously) that are commonly used in ceramics manufacturing; mixing and milling; and then adding more solvent to form a slurry having a consistency to be coated or layered onto the electrolyte. The electrode slurry typically has about 10% to about 30% volume of solid ingredients, with the remaining volume being solvent. The second electrode is then dried and sintered at 290, as discussed previously, to form a solid porous second electrode.
- It should be understood that the operations described herein may be performed in any order, unless otherwise specified, and embodiments of the disclosure may include additional or fewer operations than those disclosed herein.
- It will be further understood that the articles “a”, “an”, “the” and “said” are intended to mean that there may be one or more of the elements or steps present. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements or steps other than those expressly listed.
- The foregoing description has been presented for the purpose of illustrating certain aspects of the present disclosure and is not intended to limit the disclosure. Persons skilled in the relevant art will appreciate that many additions, modifications, variations and improvements may be implemented in light of the above teachings and still fall within the scope of the present disclosure.
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/618,474 US20170275770A1 (en) | 2015-10-08 | 2017-06-09 | Electrode-supported tubular solid-oxide electrochemical cell |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/878,544 US10458027B2 (en) | 2015-10-08 | 2015-10-08 | Electrode-supported tubular solid-oxide electrochemical cell |
US15/618,474 US20170275770A1 (en) | 2015-10-08 | 2017-06-09 | Electrode-supported tubular solid-oxide electrochemical cell |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/878,544 Division US10458027B2 (en) | 2015-10-08 | 2015-10-08 | Electrode-supported tubular solid-oxide electrochemical cell |
Publications (1)
Publication Number | Publication Date |
---|---|
US20170275770A1 true US20170275770A1 (en) | 2017-09-28 |
Family
ID=54754752
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/878,544 Expired - Fee Related US10458027B2 (en) | 2015-10-08 | 2015-10-08 | Electrode-supported tubular solid-oxide electrochemical cell |
US15/618,474 Abandoned US20170275770A1 (en) | 2015-10-08 | 2017-06-09 | Electrode-supported tubular solid-oxide electrochemical cell |
US16/574,570 Active 2036-03-10 US11021799B2 (en) | 2015-10-08 | 2019-09-18 | Electrode-supported tubular solid-oxide electrochemical cell |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/878,544 Expired - Fee Related US10458027B2 (en) | 2015-10-08 | 2015-10-08 | Electrode-supported tubular solid-oxide electrochemical cell |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/574,570 Active 2036-03-10 US11021799B2 (en) | 2015-10-08 | 2019-09-18 | Electrode-supported tubular solid-oxide electrochemical cell |
Country Status (13)
Country | Link |
---|---|
US (3) | US10458027B2 (en) |
EP (1) | EP3360190A1 (en) |
JP (1) | JP7003042B2 (en) |
KR (1) | KR20180063272A (en) |
CN (1) | CN108292769A (en) |
AU (1) | AU2015411412A1 (en) |
BR (1) | BR112018007138A8 (en) |
CA (1) | CA3001296A1 (en) |
IL (1) | IL258546A (en) |
MX (1) | MX2018004280A (en) |
RU (1) | RU2713189C2 (en) |
WO (1) | WO2017062045A1 (en) |
ZA (1) | ZA201802528B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI714202B (en) * | 2018-08-23 | 2020-12-21 | 日商昭和電工股份有限公司 | Anode for electrolytic synthesis and manufacturing method of fluorine gas |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10381645B2 (en) * | 2015-12-14 | 2019-08-13 | Bettergy Corp. | Low cost rechargeable battery and the method for making the same |
US10734656B2 (en) * | 2016-08-16 | 2020-08-04 | University Of South Carolina | Fabrication method for micro-tubular solid oxide cells |
CN110230028B (en) * | 2019-06-14 | 2021-06-29 | 深圳市致远动力科技有限公司 | Preparation method of solid film fuel cell |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020028367A1 (en) * | 2000-05-22 | 2002-03-07 | Nigel Sammes | Electrode-supported solid state electrochemical cell |
US6436565B1 (en) * | 1999-10-01 | 2002-08-20 | Korea Institute Of Energy Research | Fuel electrode-supported tubular solid oxide fuel cell and method of manufacturing the same |
WO2005057685A2 (en) * | 2003-12-02 | 2005-06-23 | Nanodynamics, Inc. | Anode-supported sofc with cermet electrolyte |
US20090148742A1 (en) * | 2007-12-07 | 2009-06-11 | Day Michael J | High performance multilayer electrodes for use in reducing gases |
US20090162723A1 (en) * | 2007-12-20 | 2009-06-25 | Zhongliang Zhan | Integrated Single-Chamber Solid Oxide Fuel Cells |
US7569292B2 (en) * | 2005-03-04 | 2009-08-04 | Toto Ltd. | Solid oxide fuel cell |
CN101786873A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院上海硅酸盐研究所 | Method for preparing electrolyte ceramic membrane of lithium ion battery |
US8580456B2 (en) * | 2010-01-26 | 2013-11-12 | Bloom Energy Corporation | Phase stable doped zirconia electrolyte compositions with low degradation |
US20140113213A1 (en) * | 2012-10-23 | 2014-04-24 | National Taiwan University | Porous oxide electrode layer and method for manufacturing the same |
US8748056B2 (en) * | 2006-10-18 | 2014-06-10 | Bloom Energy Corporation | Anode with remarkable stability under conditions of extreme fuel starvation |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5686198A (en) * | 1996-02-29 | 1997-11-11 | Westinghouse Electric Corporation | Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells |
JPH09274927A (en) * | 1996-04-03 | 1997-10-21 | Fujikura Ltd | Solid electrolyte type fuel cell |
US6605316B1 (en) | 1999-07-31 | 2003-08-12 | The Regents Of The University Of California | Structures and fabrication techniques for solid state electrochemical devices |
JP3743230B2 (en) | 1999-08-30 | 2006-02-08 | 日産自動車株式会社 | Solid electrolyte sintered body, method for producing the same, and fuel cell using the solid electrolyte sintered body |
MXPA01005771A (en) * | 1999-10-08 | 2003-07-14 | Global Thermoelectric Inc | Composite electrodes for solid state electrochemical devices. |
KR100437498B1 (en) | 2002-02-04 | 2004-06-25 | 한국에너지기술연구원 | Anode-supported tubular solid oxide fuel cell stack and fabrication method of it |
RU2236068C1 (en) * | 2003-06-10 | 2004-09-10 | Мятиев Ата Атаевич | Zirconium-based electrode-electrolyte couple (alternatives), its manufacturing process (alternatives), and organogel |
CN101107740A (en) * | 2003-12-02 | 2008-01-16 | 纳米动力公司 | Anode-supported solid oxide fuel cells using a cermet electrolyte |
JP4512788B2 (en) | 2004-02-18 | 2010-07-28 | 独立行政法人産業技術総合研究所 | High temperature steam electrolyzer |
JP5158557B2 (en) * | 2006-09-15 | 2013-03-06 | Toto株式会社 | Fuel cell structure and fuel cell including the same |
CN101207218A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Method for preparation of tubular solid-oxide fuel battery |
US7811442B2 (en) | 2007-02-10 | 2010-10-12 | N H Three LLC | Method and apparatus for anhydrous ammonia production |
JP2008305723A (en) | 2007-06-08 | 2008-12-18 | Univ Of Tokyo | Adhesive material composition, bonding method using the adhesive material composition, solid oxide fuel cell, and solid oxide steam electrolytic device |
WO2009014775A2 (en) * | 2007-07-25 | 2009-01-29 | The Regents Of The University Of California | High temperature electrochemical device with interlocking structure |
JP2009037874A (en) * | 2007-08-01 | 2009-02-19 | Central Res Inst Of Electric Power Ind | Manufacturing method of air electrode support type single cell for intermediate temperature actuating solid oxide fuel cell |
JP5520589B2 (en) | 2009-12-15 | 2014-06-11 | 日本碍子株式会社 | Manufacturing method of fuel cell |
JP2013209685A (en) | 2012-03-30 | 2013-10-10 | Nippon Shokubai Co Ltd | Electrochemical cell for ammonia production and ammonia synthesis method using the same |
JP5991581B2 (en) * | 2012-08-10 | 2016-09-14 | 国立研究開発法人物質・材料研究機構 | Electrode catalyst for oxygen electrode for solid oxide steam field cell and method for producing the same |
JP6362007B2 (en) | 2014-03-11 | 2018-07-25 | 国立大学法人九州大学 | Electrochemical cell and method for producing the same |
-
2015
- 2015-10-08 US US14/878,544 patent/US10458027B2/en not_active Expired - Fee Related
- 2015-11-10 KR KR1020187012800A patent/KR20180063272A/en unknown
- 2015-11-10 JP JP2018538523A patent/JP7003042B2/en active Active
- 2015-11-10 CN CN201580084914.3A patent/CN108292769A/en active Pending
- 2015-11-10 MX MX2018004280A patent/MX2018004280A/en unknown
- 2015-11-10 AU AU2015411412A patent/AU2015411412A1/en not_active Abandoned
- 2015-11-10 RU RU2018115736A patent/RU2713189C2/en not_active IP Right Cessation
- 2015-11-10 WO PCT/US2015/059927 patent/WO2017062045A1/en active Application Filing
- 2015-11-10 BR BR112018007138A patent/BR112018007138A8/en not_active IP Right Cessation
- 2015-11-10 CA CA3001296A patent/CA3001296A1/en not_active Abandoned
- 2015-11-10 EP EP15802248.3A patent/EP3360190A1/en not_active Withdrawn
-
2017
- 2017-06-09 US US15/618,474 patent/US20170275770A1/en not_active Abandoned
-
2018
- 2018-04-08 IL IL258546A patent/IL258546A/en unknown
- 2018-04-17 ZA ZA2018/02528A patent/ZA201802528B/en unknown
-
2019
- 2019-09-18 US US16/574,570 patent/US11021799B2/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6436565B1 (en) * | 1999-10-01 | 2002-08-20 | Korea Institute Of Energy Research | Fuel electrode-supported tubular solid oxide fuel cell and method of manufacturing the same |
US20020028367A1 (en) * | 2000-05-22 | 2002-03-07 | Nigel Sammes | Electrode-supported solid state electrochemical cell |
WO2005057685A2 (en) * | 2003-12-02 | 2005-06-23 | Nanodynamics, Inc. | Anode-supported sofc with cermet electrolyte |
US7569292B2 (en) * | 2005-03-04 | 2009-08-04 | Toto Ltd. | Solid oxide fuel cell |
US8748056B2 (en) * | 2006-10-18 | 2014-06-10 | Bloom Energy Corporation | Anode with remarkable stability under conditions of extreme fuel starvation |
US20090148742A1 (en) * | 2007-12-07 | 2009-06-11 | Day Michael J | High performance multilayer electrodes for use in reducing gases |
US20090162723A1 (en) * | 2007-12-20 | 2009-06-25 | Zhongliang Zhan | Integrated Single-Chamber Solid Oxide Fuel Cells |
CN101786873A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院上海硅酸盐研究所 | Method for preparing electrolyte ceramic membrane of lithium ion battery |
US8580456B2 (en) * | 2010-01-26 | 2013-11-12 | Bloom Energy Corporation | Phase stable doped zirconia electrolyte compositions with low degradation |
US20140113213A1 (en) * | 2012-10-23 | 2014-04-24 | National Taiwan University | Porous oxide electrode layer and method for manufacturing the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI714202B (en) * | 2018-08-23 | 2020-12-21 | 日商昭和電工股份有限公司 | Anode for electrolytic synthesis and manufacturing method of fluorine gas |
Also Published As
Publication number | Publication date |
---|---|
IL258546A (en) | 2018-05-31 |
KR20180063272A (en) | 2018-06-11 |
JP2018532891A (en) | 2018-11-08 |
MX2018004280A (en) | 2018-08-01 |
US20170101719A1 (en) | 2017-04-13 |
US10458027B2 (en) | 2019-10-29 |
BR112018007138A8 (en) | 2020-02-27 |
BR112018007138A2 (en) | 2018-11-06 |
EP3360190A1 (en) | 2018-08-15 |
JP7003042B2 (en) | 2022-01-20 |
RU2018115736A3 (en) | 2019-11-12 |
US11021799B2 (en) | 2021-06-01 |
RU2018115736A (en) | 2019-11-12 |
RU2713189C2 (en) | 2020-02-04 |
CA3001296A1 (en) | 2017-04-13 |
WO2017062045A1 (en) | 2017-04-13 |
US20200040469A1 (en) | 2020-02-06 |
AU2015411412A1 (en) | 2018-04-26 |
ZA201802528B (en) | 2020-01-29 |
CN108292769A (en) | 2018-07-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11021799B2 (en) | Electrode-supported tubular solid-oxide electrochemical cell | |
Danilovic et al. | Correlation of fuel cell anode electrocatalytic and ex situ catalytic activity of perovskites La0. 75Sr0. 25Cr0. 5X0. 5O3− δ (X= Ti, Mn, Fe, Co) | |
Liu et al. | High-performance Ni–BaZr0. 1Ce0. 7Y0. 1Yb0. 1O3− δ (BZCYYb) membranes for hydrogen separation | |
WO2006125177A2 (en) | Electrode and catalytic materials | |
CA2717285A1 (en) | Solid oxide fuel cell reactor | |
CN110050373B (en) | Solid oxide fuel cell anode | |
Gao et al. | Improve the catalytic property of La0. 6Sr0. 4Co0. 2Fe0. 8O3/Ce0. 9Gd0. 1O2 (LSCF/CGO) cathodes with CuO nanoparticles infiltration | |
JP2015172213A (en) | Electrochemical cell and method of producing the same | |
JP6625855B2 (en) | Cell for steam electrolysis and method for producing the same | |
JP6997683B2 (en) | Methods for Transporting Nitride Ions in Electrochemical Cells | |
US8377606B2 (en) | Paraffin fuel cell | |
US8039167B2 (en) | Paraffin fuel cell | |
JPWO2020004333A1 (en) | Electrode for solid oxide cell and solid oxide cell using it | |
KR20230156935A (en) | Ammonia dehydrogenation | |
JP6747778B2 (en) | Cell for steam electrolysis | |
EP3176287B1 (en) | Steam electrolysis cell | |
JP7329317B2 (en) | Electrochemical stack with solid electrolyte and method of making same | |
Raj et al. | Cogeneration of HCN in a solid oxide fuel cell | |
US11677088B2 (en) | Process for the manufacture of a solid oxide membrane electrode assembly | |
JP4748089B2 (en) | Composite type mixed conductor | |
JPH0280360A (en) | Production of functional ceramics | |
JP5228353B2 (en) | Composite type mixed conductor | |
Bansod et al. | Structural and electrochemical investigation on Ga 3+ doped Pr 1.3 Sr 0.7 Ni 0.7 Cu 0.3 O 4+ δ cathodes for IT-SOFC applications | |
CN113731314A (en) | High-temperature ceramic reactor based on joule heat and preparation method thereof | |
JPH04119924A (en) | Calcium doped lanthanum chromite powder, its sintered body, solid electrolyte type fuel cell utilizing the said sintered body and method for synthesizing said powder |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
AS | Assignment |
Owner name: LOW EMISSIONS RESOURCES CORPORATION, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ALVAREZ, FERNANDO;SAMMES, LAUREN BEVERLY;SIGNING DATES FROM 20191125 TO 20191126;REEL/FRAME:051170/0936 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STCV | Information on status: appeal procedure |
Free format text: NOTICE OF APPEAL FILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: TRANSFORMATIONAL ENERGY LIMITED, UNITED KINGDOM Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LOW EMISSIONS RESOURCES GLOBAL LTD;REEL/FRAME:062195/0922 Effective date: 20221220 Owner name: LOW EMISSIONS RESOURCES GLOBAL, LTD., SCOTLAND Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LOW EMISSIONS RESOURCES CORPORATION;REEL/FRAME:062218/0109 Effective date: 20171124 |