WO2020107027A1 - Électrodes à double porosité et procédé de fabrication - Google Patents

Électrodes à double porosité et procédé de fabrication

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Publication number
WO2020107027A1
WO2020107027A1 PCT/US2019/062879 US2019062879W WO2020107027A1 WO 2020107027 A1 WO2020107027 A1 WO 2020107027A1 US 2019062879 W US2019062879 W US 2019062879W WO 2020107027 A1 WO2020107027 A1 WO 2020107027A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
fuel cell
layer
electrolyte
anode
Prior art date
Application number
PCT/US2019/062879
Other languages
English (en)
Original Assignee
Utility Global, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US16/674,695 external-priority patent/US11735755B2/en
Priority claimed from US16/680,770 external-priority patent/US20200156104A1/en
Priority claimed from US16/684,864 external-priority patent/US11611097B2/en
Priority claimed from US16/684,838 external-priority patent/US20200144654A1/en
Application filed by Utility Global, Inc. filed Critical Utility Global, Inc.
Publication of WO2020107027A1 publication Critical patent/WO2020107027A1/fr

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    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
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    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/021—Alloys based on iron
    • H—ELECTRICITY
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    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/006—Pressing and sintering powders, granules or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
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    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • H01M8/04074—Heat exchange unit structures specially adapted for fuel cell
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

Definitions

  • This invention generally relates to electrochemical reactors. More specifically, this invention relates to electrochemical reactors with fluid dispersing components. BACKGROUND
  • a fuel cell is an electrochemical apparatus or reactor that converts the chemical energy from a fuel into electricity through an electrochemical reaction. Sometimes, the heat generated by a fuel cell is also usable.
  • fuel cells There are many types of fuel cells.
  • PEMFCs proton- exchange membrane fuel cells
  • MEA membrane electrode assemblies
  • An ink of catalyst, carbon, and electrode are sprayed or painted onto the solid electrolyte and carbon paper is hot pressed on either side to protect the inside of the cell and also act as electrodes.
  • the most important part of the cell is the triple phase boundary where the electrolyte, catalyst, and reactants mix and thus where the cell reactions actually occur.
  • the membrane must not be electrically conductive so that the half reactions do not mix.
  • PEMFCs are good candidates for vehicle and other mobile applications of all sizes (e.g., mobile phones) because they are compact.
  • water management is crucial to performance. Too much water will flood the membrane and too little will dry it. In both cases, power output will drop. Water management is a difficult problem in PEM fuel cell systems, mainly because water in the membrane is attracted toward the cathode of the cell through polarization.
  • the platinum catalyst on the membrane is easily poisoned by carbon monoxide (CO level needs to be no more than one part per million).
  • CO level carbon monoxide
  • the membrane is also sensitive to things like metal ions which can be introduced by corrosion of metallic bipolar plates, metallic components in the fuel cell system or from contaminants in the fuel and/or oxidant.
  • Solid oxide fuel cells are a different class of fuel cells that use a solid oxide material as the electrolyte.
  • SOFCs use a solid oxide electrolyte to conduct negative oxygen ions from the cathode to the anode.
  • the electrochemical oxidation of the oxygen ions with fuel e.g., hydrogen, carbon monoxide
  • fuel e.g., hydrogen, carbon monoxide
  • Some SOFCs use proton conducting electrolytes (PC-SOFCs) which transport protons instead of oxygen ions through the electrolyte.
  • PC-SOFCs proton conducting electrolytes
  • SOFCs using oxygen ion conducting electrolytes have higher operating temperatures than PC-SOFCs.
  • SOFCs do not typically require expensive platinum catalyst materials which are typically necessary for lower temperature fuel cells (i.e., PEMFCs), and are not vulnerable to carbon monoxide catalyst poisoning.
  • Solid oxide fuel cells have a wide variety of applications, such as auxiliary power units for homes and vehicles as well as stationary power generation units for data centers.
  • SOFCs comprise interconnects, which are placed between each individual cell so that the cells are connected in series and that the electricity generated by each cell is combined.
  • One category of SOFCs are segmented-in-series (SIS) type SOFCs. The electrical current flow in SIS type SOFCs is parallel to the electrolyte in the lateral direction. Contrary to the SIS type SOFC, a different category of SOFC has electrical current flow perpendicular to the electrolyte in the lateral direction.
  • BOP balance of plant
  • the mechanical balance of plant includes air preheater, reformer and/or pre-reformer, afterburner, water heat exchanger and anode tail gas oxidizer.
  • Other components are also needed, such as, power electronics, hydrogen sulfide sensors and fans for electrical balance of plant.
  • BOP components are often complex and expensive. Fuel cells and fuel cell systems are simply examples of the necessity and interest to develop advanced manufacturing systems and methods such that these efficient systems may be economically produced and widely deployed.
  • heating/curing/sintering steps are often dissociated with one another.
  • an integrated deposition and heating process that may significantly reduce manufacturing complexity and cost.
  • the invention is an electrode for use in an electrochemical reactor.
  • the electrode has an electrode porosity and includes an electrode material with a material porosity, wherein the electrode has channels formed therein.
  • the porosity of the electrode material is less than the porosity of the electrode.
  • porosity of the electrode is at least 5% greater than the material porosity, more preferably at least 20% greater.
  • the electrode has a total volume and the channels have a channel volume, with the ratio as a percentage of the channel volume to the total volume is from 1 to 90%, or from 5 to 50 % or from 10 to 30%. In still another aspect, the ratio as a percentage of the channel volume to the total volume is at least 5% or at least 10% or at least 20% or at least 30% or at least 40% or at least 50%.
  • the material porosity is in the range of 20-60%, or 30-50%, or 30-40%.
  • the electrode has a thickness of no greater than 100 microns or no greater than 80 microns or no greater than 60 microns.
  • an electrode for an electrochemical reactor is made by depositing a first composition including a first electrode material and a first pore former, wherein the first pore former is a first volume fraction VFpl of the first composition.
  • a second composition is deposited with includes a second electrode material and a second pore former.
  • the second pore former is a second volume fraction VFp2.
  • the first composition and second composition form a first layer of the electrode. This first layer is heated such that at least a portion of the first pore former and at least a portion of the second pore former become empty spaces in the electrode.
  • the first electrode material and the second electrode material are the same.
  • the heating causes reduction reactions, oxidation reactions, melting, vaporization or combinations thereof.
  • This heating can be performed using a furnace, a hot fluid, a heating element, infrared radiation, electromagnetic radiation, xenon lamp, or combinations thereof.
  • this method aspect of the invention makes use of printing, extrusion, additive manufacturing, tape casting, spraying, sputtering, or screen printing.
  • the first pore former and/or the second pore former has an average diameter in the range of 10 nm to 1 mm or 100 nm to 100 microns or 500 nanometers to 50 microns.
  • the first pore former and/or the second pore former comprises carbon, graphite, graphene, polymethyl methacrylate, cellulose, metal oxides, nano diamonds, or combinations thereof.
  • At least a portion of the empty spaces caused by the first pore former or the second pore former or both become channels in the first layer.
  • the first layer has a total volume and the channels have a channel volume, with the ratio as a percentage of the channel volume to the total volume being from 1 to 90%, or from 5 to 50 % or from 10 to 30%.
  • the ratio as a percentage of the channel volume to the total volume is at least 5% or at least 10% or at least 20% or at least 30% or at least 40% or at least 50%.
  • the first layer has dual porosities, a material porosity and a layer porosity.
  • the material porosity is in the range of 20-60%, or 30-50%, or 30- 40%.
  • the electrode preferably has a thickness of no greater than 100 microns or 80 microns or 60 microns.
  • Fig. 1 illustrates a fuel cell component comprising an anode, an electrolyte and a cathode
  • Fig. 2 illustrates a fuel cell component comprising an anode, an electrolyte, a barrier layer and a cathode;
  • FIG. 3 illustrates a fuel cell component comprising an anode, a catalyst, an electrolyte, a barrier layer and a cathode;
  • Fig. 4 illustrates a fuel cell component comprising an anode, a catalyst, an electrolyte, a barrier layer, a cathode and an interconnect;
  • FIG. 5 schematically illustrates two fuel cells in a fuel cell stack
  • FIG. 6 illustrates a system for integrated deposition and heating using electromagnetic radiation (EMR);
  • Fig. 7 graphically illustrates strain rate tensors (SRTs) of a first composition and a second composition as a function of temperature;
  • Fig. 8 illustrates a process flow for forming and heating at least a portion of a fuel cell
  • Fig. 9 illustrates maximum height profile roughness of an anode or cathode surface
  • FIG. 10A illustrates an electrochemical (EC) gas producer
  • Fig. 10B illustrates an EC gas producer
  • Fig. IOC illustrates an electrochemical compressor comprising anodes, electrolytes, cathodes, porous bipolar plates, a fluid distributor on one end and a fluid collector on the opposing end;
  • FIG. 11A illustrates a perspective view of a fuel cell cartridge (FCC);
  • FIG. 11B illustrates cross-sectional views of a fuel cell cartridge (FCC);
  • Fig. llC illustrates top view and bottom view of a fuel cell cartridge (FCC);
  • Fig. 12 is a scanning electron microscopy image (side view) illustrating an electrolyte (YSZ) printed and sintered on an electrode (NiO-YSZ);
  • FIG. 13A illustrates an impermeable interconnect 1302 with a fluid dispersing component 1304;
  • Fig. 13B illustrates an impermeable interconnect 1302 with two fluid dispersing components 1304;
  • Fig. 13C illustrates segmented fluid dispersing components 1304 of similar shapes but different sizes on an impermeable interconnect 1302;
  • Fig. 13D illustrates segmented fluid dispersing components 1304 of similar shapes and similar sizes on an impermeable interconnect 1302;
  • Fig. 13E illustrates segmented fluid dispersing components 1304 of similar shapes and similar sizes but closely packed on an impermeable interconnect 1302;
  • Fig. 13F illustrates segmented fluid dispersing components 1304 of different shapes and different sizes on an impermeable interconnect 1302;
  • Fig. 13G illustrates an impermeable interconnect 1302 and fluid dispersing component segment 1304;
  • Fig. 13H illustrates an impermeable interconnect 1302 and fluid dispersing component segment 1304;
  • Fig. 131 illustrates an impermeable interconnect 1302 and fluid dispersing component segments 1306, 1308;
  • Fig. 13J illustrates an impermeable interconnect 1302 and a fluid dispersing component segment 1304;
  • Fig. 13K illustrates a fluid dispersing component 1304
  • Fig. 14A illustrates a template 1400 for making channeled electrodes
  • Fig. 14B is a cross-sectional view of a half cell between a first interconnect and an electrolyte
  • Fig. 14C is a cross-sectional view of a half cell between a second interconnect and an electrolyte
  • Fig. 14D is a cross-sectional view of a half cell between a first interconnect and an electrolyte
  • Fig. 14E is a cross-sectional view of a half cell between a second interconnect and an electrolyte
  • FIG. 15A schematically illustrates segments offluid dispersing components in a first layer
  • FIG. 15B schematically illustrates fluid dispersing components in a first layer along with a second layer
  • FIG. 15C schematically illustrates fluid dispersing components in a first layer along with a second and third layer
  • FIG. 15D schematically illustrates fluid dispersing components in a first layer along with a second layer
  • Fig. 16 is an illustrative example of an electrode having dual porosities.
  • FIG. 17 schematically illustrates an example of a half cell in an EC reactor.
  • Electrochemical reactors include solid oxide fuel cells, solid oxide fuel cell stacks, electrochemical gas producers, electrochemical compressors, solid state batteries, or solid oxide flow batteries.
  • the materials used in the electrodes may have a first porosity wherein the electrodes have a second porosity formed by, for example, channels formed into the electrodes.
  • the layers of the electrode may have dual porosities.
  • the electrodes may comprise one or more layers wherein each layer is made of materials of different compositions, porosities and thicknesses and each layer of the electrode may have different porosities formed from channels, pores or other means.
  • Embodiments herein also describe methods to form layers of the electrode. These methods may include one or more of deposition, printing, extrusion, additive manufacturing, tape casting, spraying, sputtering, or screen printing. Heating methods are also disclosed which include a furnace, a hot fluid, a heating element, infrared radiation, electromagnetic radiation, xenon lamp, or combinations thereof. These heating methods may induce reduction reactions or oxidation reactions or melting or vaporization or combinations thereof.
  • Embodiments disclosed herein are methods to make pores in the electrode layers.
  • pore formers may be used. Pore formers may be added during deposition steps of the layers of the electrode to impart porosity in the electrode layers.
  • compositions and materials are used interchangeably unless otherwise specified. Each composition/material may have multiple elements, phases, and components. Heating as used herein refers to actively adding energy to the compositions or materials.
  • the term "in situ" in this disclosure refers to the treatment (e.g., heating) process being performed either at the same location or in the same device of the forming process of the compositions or materials.
  • the deposition process and the heating process are performed in the same device and at the same location, in other words, without changing the device and without changing the location within the device.
  • the deposition process and the heating process are performed in the same device at different locations, which is also considered in situ.
  • a major face of an object is the face of the object that has a surface area larger than the average surface area of the object, wherein the average surface area of the object is the total surface area of the object divided by the number of faces of the object.
  • a major face refers to a face of an item or object that has a larger surface area than a minor face.
  • a major face is the face or surface in the lateral direction.
  • strain rate tensor or "SRT” is meant to refer to the rate of change of the strain of a material in the vicinity of a certain point and at a certain time. It can be defined as the derivative of the strain tensor with respect to time. When SRTs or difference of SRTs are compared in this disclosure, it is the magnitude that is being used.
  • lateral refers to the direction that is perpendicular to the stacking direction of the layers in a non-SIS type fuel cell.
  • lateral direction refers to the direction that is perpendicular to the stacking direction of the layers in a fuel cell or the stacking direction of the slices to form an object during deposition.
  • Lateral also refers to the direction that is the spread of deposition process.
  • Syngas i.e., synthesis gas in this disclosure refers to a mixture consisting primarily of hydrogen, carbon monoxide and carbon dioxide.
  • absorbance is a measure of the capacity of a substance to absorb electromagnetic radiation (EMR) of a wavelength.
  • Absorption of radiation refers to the energy absorbed by a substance when exposed to the radiation.
  • An interconnect in an electrochemical device is often either metallic or ceramic that is placed between the individual cells or repeat units. Its purpose is to connect each cell or repeat unit so that electricity can be distributed or combined.
  • An interconnect is also referred to as a bipolar plate in an electrochemical device.
  • An interconnect being an impermeable layer as used herein refers to it being a layer that is impermeable to fluid flow.
  • an impermeable layer has a permeability of less than 1 micro darcy, or less than 1 nano darcy.
  • an interconnect having no fluid dispersing element refers to an interconnect having no elements (e.g., channels) to disperse a fluid.
  • a fluid may comprise a gas or a liquid or a mixture of a gas and a liquid.
  • Such fluids may include one or more of hydrogen, methane, ethane, propane, butane, oxygen, ambient air or light hydrocarbons (i.e., pentane, hexane, octane).
  • Such an interconnect may have inlets and outlets (i.e., openings) for materials or fluids to pass through.
  • microchannels are used interchangeably with microfluidic channels or microfluidic flow channels.
  • sintering refers to a process to form a solid mass of material by heat or pressure, or a combination thereof, without melting the material to the extent of liquefaction.
  • material particles are coalesced into a solid or porous mass by being heated, wherein atoms in the material particles diffuse across the boundaries of the particles, causing the particles to fuse together and form one solid piece.
  • T sinter refers to the temperature at which this phenomenon begins to take place.
  • pore former is intended to have a relatively broad meaning. "Pore former” may be referring to any particulate material that is included in a composition during formation, which may partially or completely vacate a space by a process, such as heating, combustion or vaporizing.
  • electrically conductive component is intended to refer to components in a fuel cell, such as electrodes and interconnects, that are electrically conductive.
  • SOFCs solid oxide fuel cells
  • electrochemical devices or reactors includes electrochemical (EC) gas producer electrochemical (EC) compressor, solid oxide fuel cells, solid oxide fuel cell stack, solid state battery, or solid oxide flow battery.
  • an electrochemical reactor comprises solid oxide fuel cell, solid oxide fuel cell stack, electrochemical gas producer, electrochemical compressor, solid state battery, or solid oxide flow battery.
  • Catalysts include Fischer Tropsch (FT) catalysts or reformer catalysts.
  • Reactor/vessel includes FT reactor or heat exchanger.
  • a method comprising depositing a composition on a substrate slice by slice (this may also be described as line-by-line deposition) to form an object; heating in situ the object using electromagnetic radiation (EMR); wherein said composition comprises a first material and a second material, wherein the second material has a higher absorbance ofEMR than the first material.
  • EMR electromagnetic radiation
  • heating may cause an effect comprising drying, curing, sintering, annealing, sealing, alloying, evaporating, restructuring, foaming or combinations thereof.
  • the EMR has a peak wavelength ranging from 10
  • the EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser or electron beam.
  • Fig. 6 illustrates a system for integrated deposition and heating using electromagnetic radiation (EMR).
  • Fig. 6 further illustrates system 600 an object 603 on a receiver 604 formed by deposition nozzles 601 and EMR 602 for heating in situ, according to an embodiment of this disclosure.
  • Receiver 604 may be a platform that moves and may further receive deposition, heat, irradiation, or combinations thereof.
  • Receiver 604 may also be referred to as a chamber wherein the chamber may be completely enclosed, partially enclosed or completely open to the atmosphere.
  • the first material comprises yttria-stabilized zirconia (YSZ), 8YSZ (8mol% YSZ powder), yttrium, zirconium, gadolinia-doped ceria (GDC or CGO), samaria-doped ceria (SDC), scandia-stabilized zirconia (SSZ), lanthanum strontium manganite (LSM), lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel, NiO, NiO-YSZ, Cu-CGO, CU2O, CuO, cerium, copper, silver, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel or combinations thereof.
  • YSZ yttria-stabilized zirconia
  • 8YSZ 8mol% YS
  • the first material comprises YSZ, SSZ, CGO, SDC, NiO-YSZ, LSM-YSZ, CGO-LSCF, doped lanthanum chromite, stainless steel or combinations thereof.
  • the second material comprises carbon, nickel oxide, nickel, silver, copper, CGO, SDC, NiO-YSZ, NiO-SSZ, LSCF, LSM, doped lanthanum chromite ferritic steels or combinations thereof.
  • object 603 comprises a catalyst, a catalyst support, a catalyst composite, an anode, a cathode, an electrolyte, an electrode, an interconnect, a seal, a fuel cell, an electrochemical gas producer, an electrolyser, an electrochemical compressor, a reactor, a heat exchanger, a vessel or combinations thereof.
  • the second material may be deposited in the same slice as the first material. In other embodiments, the second material may be deposited in a slice adjacent another slice that contains the first material. In some embodiments, said heating may remove at least a portion of the second material. In preferred embodiments, said heating leaves minimal residue of the second material such that there is no significant residue that would interfere with the subsequent steps in the process or the operation of the device being constructed. More preferably, this leaves no measurable reside of the portion of the second material.
  • the second material may add thermal energy to the first material during heating.
  • the second material has a radiation absorbance that is at least 5 times that of the first material; the second material has a radiation absorbance that is at least 10 times that of the first material; the second material has a radiation absorbance that is at least 50 times that of the first material or the second material has a radiation absorbance that is at least 100 times that of the first material.
  • the second material may have a peak absorbance wavelength no less than 200 nm, or 250 nm, or 300 nm, or 400 nm, or 500 nm.
  • the first material has a peak absorbance wavelength no greater than 700 nm, or 600 nm, or 500 nm, or 400 nm, or 300 nm.
  • the EMR has a peak wavelength no less than 200 nm, or 250 nm, or 300 nm, or 400 nm, or 500 nm.
  • the second material may comprise carbon, nickel oxide, nickel, silver, copper, CGO, NiO-YSZ, LSCF, LSM, ferritic steels, other metal oxides or combinations thereof.
  • the ferritic steel is Crofer 22 APU.
  • the first material comprises YSZ, CGO, NiO-YSZ, LSM-YSZ, other metal oxides or combinations thereof.
  • the second material comprises LSCF, LSM, carbon, nickel oxide, nickel, silver, copper, or steel.
  • carbon comprises graphite, graphene, carbon nanoparticles, nano diamonds or combinations thereof.
  • the deposition method comprises material jetting, binder jetting, inkjet printing, aerosol jetting, aerosol jet printing, vat photopolymerization, powder bed fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing or combinations thereof.
  • the deposition method further comprises one or more of the steps of controlling distance from the EMR to the receiver, EMR energy density, EMR spectrum, EMR voltage, EMR exposure duration, EMR exposure area, EMR exposure volume, EMR burst frequency, EMR exposure repetition number.
  • the object does not change location between the deposition and heating steps.
  • the EMR has a power output of no less than 1 W, or 10 W, or 100 W, or 1000 W.
  • a system comprising at least one deposition nozzle, an electromagnetic radiation (EMR) source and a deposition receiver, wherein the deposition receiver is configured to receive EMR exposure and deposition at the same location.
  • the receiver is configured such that it receives deposition for a first time period, moves to a different location in the system to receive EMR exposure for a second time period.
  • AM additive manufacturing
  • AM may also be referred to as additive fabrication, additive processes, additive techniques, additive layer manufacturing, layer manufacturing or freeform fabrication.
  • AM is extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition, lamination, direct metal laser sintering (DMLS), selective laser sintering (SLS), selective laser melting (SLM), directed energy deposition (DED), laser metal deposition (LMD), electron beam (EBAM) and metal binder jetting.
  • DMLS direct metal laser sintering
  • SLS selective laser sintering
  • SLM selective laser melting
  • DED directed energy deposition
  • LMD laser metal deposition
  • EBAM electron beam
  • a 3D printer is a type of AM machine (AMM).
  • An inkjet printer or ultrasonic inkjet printer are additional examples of AMMs.
  • the invention is a method of making a fuel cell comprising: (a) producing an anode using an AMM; (b) creating an electrolyte using the AMM; and (c) making a cathode using the AMM.
  • the anode, the electrolyte and the cathode are assembled into a fuel cell utilizing an AMM in addition to other steps that are not completed using an AMM.
  • the fuel cell is formed using only the AMM.
  • steps (a), (b), and (c) exclude tape casting and screen printing.
  • the method of assembling a fuel cell with an AMM excludes compression in assembling.
  • the layers are deposited one on top of another in a step wise manner such that assembling is accomplished at the same time as deposition.
  • the methods described herein are useful in making planar fuel cells.
  • the methods described herein are also useful in making fuel cell, wherein electrical current flow is perpendicular to the electrolyte in the lateral direction when the fuel cell is in use.
  • the interconnect, the anode, the electrolyte, and the cathode are formed layer on layer, for example, printed layer on layer. It is important to note that, within the scope of the invention, the order of forming these layers can be varied. In other words, either the anode or the cathode can be formed before the other. Naturally, the electrolyte is formed so that it is between the anode and the cathode. Barrier layer(s), catalyst layer(s) and interconnect(s) are formed so as to lie in the appropriate position within the fuel cell to perform their functions.
  • each of the interconnect, the anode, the electrolyte and the cathode has six faces.
  • the anode is printed on the interconnect and is in contact with the interconnect;
  • the electrolyte is printed on the anode and is in contact with the anode;
  • the cathode is printed on the electrolyte and is in contact with the electrolyte.
  • Each print may be sintered, for example, using EMR.
  • the AM method comprises making at least one barrier layer using the AMM.
  • the at least one barrier layer may be located between the electrolyte and the cathode or between the electrolyte and the anode or both.
  • the at least one barrier layer may be assembled with the anode, the electrolyte and the cathode using the AMM. In some embodiments, no barrier layer is needed or utilized in the fuel cell.
  • the AM method comprises making an interconnect using the AMM.
  • the interconnect may be assembled with the anode, the electrolyte and the cathode using the AMM.
  • the AMM forms a catalyst and incorporates said catalyst into the fuel cell.
  • the anode, the electrolyte, the cathode and the interconnect are made at a temperature above 100 °C.
  • the AM method comprises heating the fuel cell, wherein said fuel cell comprises the anode, the electrolyte, the cathode, the interconnect and optionally at least one barrier layer.
  • the fuel cell comprises a catalyst.
  • the method comprises heating the fuel cell to a temperature above 500 °C.
  • the fuel cell is heated using one or both of EMR or oven curing.
  • the AMM utilizes a multi-nozzle additive manufacturing method.
  • the multi-nozzle additive manufacturing method comprises nanoparticle jetting.
  • a first nozzle delivers a first material
  • a second nozzle delivers a second material
  • a third nozzle delivers a third material.
  • particles of a fourth material are placed in contact with a partially constructed fuel cell and bonded to the partially constructed fuel cell using a laser, photoelectric effect, light, heat, polymerization or binding.
  • the anode, the cathode or the electrolyte comprises a first, second, third or fourth material.
  • the AMM performs multiple AM techniques.
  • the AM techniques comprise one or more of extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition or lamination.
  • AM is a deposition technique comprising material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing, vat photopolymerization, powder bed fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing or combinations thereof.
  • an AM method of making a fuel cell stack comprising: (a) producing an anode using an additive manufacturing machine (AMM); (b) creating an electrolyte using the AMM; (c) making a cathode using the AMM; (d) making an interconnect using the AMM; wherein the anode, the electrolyte, the cathode, and the interconnect form a first fuel cell; (e) repeating steps (a)-(d) to make a second fuel cell; and (f) assembling the first fuel cell and the second fuel cell into a fuel cell stack.
  • AMM additive manufacturing machine
  • the first fuel cell and the second fuel cell are formed from the anode, the electrolyte, the cathode and the interconnect utilizing the AMM.
  • the fuel cell stack is formed using only the AMM.
  • steps (a)-(f) exclude one or both of tape casting and screen printing.
  • the AM method comprises making at least one barrier layer using the AMM.
  • the at least one barrier layer is located between the electrolyte and the cathode or between the electrolyte and the anode or both for the first fuel cell and the second fuel cell.
  • steps (a)-(d) are performed at a temperature above 100 °C. In other embodiments, steps (a)-(d) are performed at a temperature in the range of 100 °C to 500 °C. In some embodiments, the AMM makes a catalyst and incorporates said catalyst into the fuel cell stack.
  • the AM method comprises heating the fuel cell stack. In an embodiment, the AM method comprises heating the fuel cell stack to a temperature above 500 °C. In some embodiments, the fuel cell stack is heated using EMR and/or oven curing. In some embodiments, the laser has a laser beam, wherein the laser beam is expanded to create a heating zone with uniform power density. In some embodiments, the laser beam is expanded by utilizing one or more mirrors. In some embodiments, each layer of the fuel cell may be cured separately by EMR. In some embodiments, a combination of one or more fuel cell layers may be cured together by EMR. In some embodiments, the first fuel cell is EMR cured, assembled with the second fuel cell, and then the second fuel cell is EMR cured.
  • the first fuel cell is assembled with the second fuel cell, and then the first fuel cell and the second fuel cell are cured separately by EMR.
  • the first fuel cell and the second fuel cell may be cured separately by EMR, and then the first fuel cell is assembled with the second fuel cell to form a fuel cell stack.
  • the first fuel cell is assembled with the second fuel cell to form a fuel cell stack, and then the fuel cell stack may be cured by EMR.
  • an AM method of making a multiplicity of fuel cells comprising (a) producing a multiplicity of anodes simultaneously using an additive manufacturing machine (AMM); (b) creating a multiplicity of electrolytes using the AMM simultaneously; and (c) making a multiplicity of cathodes using the AMM simultaneously.
  • the anodes, the electrolytes and cathodes are assembled into fuel cells utilizing the AMM simultaneously.
  • the fuel cells are formed using only the AMM.
  • the method comprises making at least one barrier layer using the AMM for each of the multiplicity of fuel cells simultaneously.
  • the at least one barrier layer may be located between the electrolyte and the cathode or located between the electrolyte and the anode, or both.
  • the at least one barrier layer may be assembled with the anode, the electrolyte and the cathode using the AMM for each fuel cell.
  • the method comprises making an interconnect using the AMM for each of the multiplicity of fuel cells simultaneously.
  • the interconnect may be assembled with the anode, the electrolyte and the cathode using the AMM for each fuel cell.
  • the AMM forms a catalyst for each of the multiplicity of fuel cells simultaneously and incorporates said catalyst into each of the fuel cells.
  • heating each layer or heating a combination of layers of the multiplicity of fuel cells takes place
  • the multiplicity of fuel cells may include two or more fuel cells.
  • the AMM uses two or more different nozzles to jet or print different materials at the same time.
  • a first nozzle deposits an anode layer for fuel cell 1
  • a second nozzle deposits a cathode layer for fuel cell 2
  • a third nozzle deposits an electrolyte for fuel cell 3, at the same time.
  • a first nozzle deposits an anode for fuel cell 1
  • a second nozzle deposits a cathode for fuel cell 2
  • a third nozzle deposits an electrolyte for fuel cell 3
  • a fourth nozzle deposits an interconnect for fuel cell 4, at the same time.
  • AMM additive manufacturing machine
  • Said chamber is able to withstand
  • said chamber enables production of the fuel cells.
  • the chamber enables heating of the fuel cells in situ as the components of the fuel cell are being deposited.
  • the chamber may be heated by laser, electromagnetic waves/electromagnetic radiation (EMR), hot fluid or a heating element associated with the chamber, or combinations thereof.
  • the heating element may comprise a heated surface, heating coil or a heating rod.
  • said chamber may be configured to apply pressure to the fuel cells inside. The pressure may be applied via a moving element associated with the chamber.
  • the moving element may be a moving stamp or plunger.
  • said chamber may be configured to withstand pressure the chamber may be configured to be pressurized or depressurized by a fluid. The fluid in the chamber may be changed or replaced when needed.
  • the chamber may be enclosed. In some cases, the chamber may be sealed. In some cases, the chamber may be open to ambient atmosphere or to a controlled atmosphere. In some cases, the chamber may be a platform without top and side walls.
  • system 600 comprises deposition nozzles or material jetting nozzles 601, EMR source 602 (e.g., xenon lamp),; object being formed 603, and chamber or receiver 604 as a part of an AMM.
  • EMR source 602 e.g., xenon lamp
  • the chamber or receiver 604 is configured to receive both deposition from nozzles and radiation from EMR source 602.
  • deposition nozzles 601 may be movable.
  • the chamber or receiver 604 may be movable.
  • EMR source 602 is movable.
  • the object comprises a catalyst, a catalyst support, a catalyst composite, an anode, a cathode, an electrolyte, an electrode, an interconnect, a seal, a fuel cell, an electrochemical gas producer, an electrolyser, an electrochemical compressor, a reactor, a heat exchanger, a vessel or combinations thereof.
  • AM techniques suitable for this disclosure comprise extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition and lamination.
  • extrusion may be used for AM.
  • Extrusion AM involves the spatially controlled deposition of material (e.g., thermoplastics).
  • Extrusion AM may also referred to as fused filament fabrication (FFF) or fused deposition modeling (FDM) in this disclosure.
  • FFF fused filament fabrication
  • FDM fused deposition modeling
  • AM comprises photopolymerization (i.e., stereolithography (SLA)) for the process of this disclosure.
  • SLA involves spatially-defined curing of a photoactive liquid (a "photoresin"), using a scanning laser or a high-resolution projected image, and transforming the photoactive liquid into a crosslinked solid.
  • Photopolymerization can produces parts with details and dimensions ranging from the micrometer- to meter-scales.
  • AM comprises powder bed fusion (PBF).
  • PBF AM processes build objects by melting powdered feedstock, such as a polymer or metal. PBF processes begin by spreading a thin layer of powder across a build area. Cross-sections are then melted a layer at a time, most often using a laser, electron beam or intense infrared lamps.
  • PBF of metals may use selective laser melting (SLM) or electron beam melting (EBM).
  • SLS of polymers may use selective laser sintering (SLS).
  • SLS systems may print thermoplastic polymer materials, polymer composites or ceramics.
  • SLM systems may be suitable for a variety of pure metals and alloys, wherein the alloys are compatible with rapid solidification that occurs in SLM.
  • AM may comprise material jetting.
  • AM by material jetting may be accomplished by depositing small drops (or droplets) of material with spatial control.
  • material jetting is performed three dimensionally (3D), two
  • Binder jetting AM involves inkjet deposition of a liquid binder onto a powder bed. In some cases, binder jetting is combined with other AM processes, such as for example, spreading of powder to make the powder bed (analogous to SLS/SLM) and inkjet printing.
  • AM comprises directed energy deposition (DED).
  • DED directed energy deposition
  • the DED process uses a directed flow of powder or a wire feed, along with an energy intensive source such as laser, electric arc or electron beam.
  • DED is a direct-write process, wherein the location of material deposition is determined by movement of the deposition head which allows large metal structures to be built without the constraints of a powder bed.
  • AM comprises lamination AM or laminated object
  • consecutive layers of sheet material are consecutively bonded and cut in order to form a 3D structure.
  • Traditional methods of manufacturing a fuel cell stack can comprise over 100 steps. These steps may include, but not limited to, milling, grinding, filtering, analyzing, mixing, binding, evaporating, aging, drying, extruding, spreading, tape casting, screen printing, stacking, heating, pressing, sintering and compressing.
  • the methods disclosed herein describe manufacturing of a fuel cell or fuel cell stack using one AMM.
  • the AMM of this disclosure preferably performs both extrusion and ink jetting to manufacture a fuel cell or fuel cell stack.
  • Extrusion may be used to manufacture thicker layers of a fuel cell, such as, the anode and/or the cathode.
  • Ink jetting may be used to manufacture thin layers of a fuel cell.
  • Ink jetting may be used to manufacture the electrolyte.
  • the AMM may operate at temperature ranges sufficient to enable curing in the AMM itself. Such temperature ranges are 100 °C or above, 100 - 300 °C or 100 - 500 °C.
  • all layers of a fuel cell are formed and assembled via printing.
  • the material for making the anode, cathode, electrolyte and the interconnect, respectively, may be made into an ink form comprising a solvent and particles (e.g., nanoparticles).
  • aqueous inks There are two categories of ink formulations - aqueous inks and non-aqueous inks.
  • the aqueous ink comprises an aqueous solvent (e.g., water, deionized water), particles, dispersant and a surfactant.
  • the aqueous ink comprises an aqueous solvent, particles, dispersant, surfactant but no polymeric binder.
  • the aqueous ink may optionally comprise a co-solvent, such as an organic miscible solvent (methanol, ethanol, isopropyl alcohol). Such co-solvents preferably have a lower boiling point than water.
  • the dispersant may be an electrostatic dispersant, steric dispersant, ionic dispersant, or a non-ionic dispersant, or a combination thereof.
  • the surfactant may preferably be non-ionic, such as an alcohol alkoxylate or an alcohol ethoxylate.
  • the non-aqueous ink may comprise an organic solvent (e.g., methanol, ethanol, isopropyl alcohol, butanol) and particles.
  • CGO powder is mixed with water to form an aqueous ink further comprising a dispersant and a surfactant but with no polymeric binder added.
  • the CGO fraction based on mass (herein expressed as weight % (wt%)) is in the range of 10 wt% to 25 wt%.
  • CGO powder is mixed with ethanol to form a non-aqueous ink further comprising polyvinyl butaryl added with the CGO fraction in the range of 3 wt% to 30 wt%.
  • LSCF is mixed with n-butanol or ethanol to form a non-aqueous ink further comprising polyvinyl butaryl with the LSCF fraction in the range of 10 wt% to 40 wt%.
  • YSZ particles are mixed with water to form an aqueous ink further comprising a dispersant and surfactant but with no polymeric binder added.
  • the YSZ fraction is in the range of 3 wt% to 40 wt%.
  • NiO particles are mixed with water to form an aqueous ink further comprising a dispersant and surfactant but with no polymeric binder added with the NiO fraction in the range of 5 wt% to 25 wt%.
  • LSCF or LSM particles are dissolved in a solvent, wherein the solvent is water or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used in other examples.
  • LSCF is deposited (e.g., printed) into a layer.
  • a xenon lamp may be used to irradiate the LSCF layer with EMR to sinter the LSCF particles.
  • the xenon flash lamp may be a 10 kW unit applied at a voltage of 400V and a frequency of 10 Hz for a total exposure duration of 1000 ms.
  • YSZ particles are mixed with a solvent, wherein the solvent is water (e.g., de-ionized water) or an alcohol (e.g., butanol) or a mixture of alcohols.
  • the solvent is water (e.g., de-ionized water) or an alcohol (e.g., butanol) or a mixture of alcohols.
  • Organic solvents other than alcohols may also be used in other examples.
  • metallic particles e.g., silver nanoparticles
  • the solvent may comprise water (e.g., de-ionized water) and an organic solvent.
  • the organic solvent may comprise mono-, di-, or tri-ethylene glycols or higher ethylene glycols, propylene glycol, 1,4- butanediol or ethers of such glycols, thiodiglycol, glycerol and ethers and esters thereof, polyglycerol, mono-, di-, and tri-ethanolamine, propanolamine, N,N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, 1,3-dimethylimidazolidone, methanol, ethanol, isopropanol, n-propanol, diacetone alcohol, acetone, methyl ethyl ketone or propylene carbonate, or combinations thereof.
  • CGO particles are dissolved in a solvent, wherein the solvent may be water (e.g., de-ionized water) or an alcohol.
  • the alcohol may comprise methanol, ethanol, butanol or a mixture of alcohols.
  • Organic solvents other than alcohols may also be used.
  • CGO may be used as barrier layer for LSCF.
  • YSZ may also be used as a barrier layer for LSM.
  • no polymeric binder may be added to the aqueous inks.
  • a method of making a fuel cell comprises using only one AMM to manufacture a fuel cell, wherein the fuel cell comprises an anode, electrolyte and a cathode.
  • the fuel cell comprises at least one barrier layer, for example, between the electrolyte and the cathode, or between the electrolyte and the cathode, or both.
  • the at least one barrier layer is preferably also made by the same AMM.
  • the AMM may also produce an interconnect and assembles the interconnect with the anode, cathode, at least one barrier layer and the electrolyte.
  • asingle AMM makes a first fuel cell, wherein the fuel cell comprises an anode, electrolyte, cathode, at least one barrier layer and an interconnect.
  • a single AMM makes a second fuel cell.
  • a single AMM is used to assemble a first fuel cell with a second fuel cell to form a fuel cell stack.
  • the production of fuel cells using an AMM is repeated as many times as desired.
  • a fuel cell stack comprising two or more fuel cells is thus assembled using an AMM.
  • the various layers of the fuel cell are produced by an AMM above ambient temperature.
  • the temperatures may be above 100 °C, in the range of 100 °C to 500 °C or in the range of 100 °C to 300 °C.
  • a fuel cell or fuel cell stack is heated after it is assembled.
  • the fuel cell or fuel cell stack is heated at a temperature above 500 °C.
  • the fuel cell or fuel cell stack is heated at a temperature in the range of 500 °C to 1500 °C.
  • an AMM comprises a chamber where the manufacturing of fuel cells takes place.
  • This chamber may be able to withstand high temperature to enable the production of the fuel cells wherein the high temperature is at least 300 °C, at least 500 °C, at least 1000 °C or at least 1500 °C.
  • this chamber may also enable the heating of the fuel cells to take place in the chamber.
  • Various heating methods may be applied, such as laser heating/curing, electromagnetic wave heating, hot fluid heating or one or more heating elements associated with the chamber.
  • the heating element may be a heating surface, heating coil or a heating rod and is associated with the chamber such that the content in the chamber is heated to the desired temperature range.
  • the chamber of the AMM may also be able to apply pressure to the fuel cell(s) inside.
  • a pressure may be applied via a moving element, such as a moving stamp or plunger.
  • the chamber of the AMM is able to withstand pressure.
  • the chamber can be pressurized or depressurized as desired by a fluid.
  • the fluid in the chamber can also be changed or replaced as needed.
  • a fuel cell or fuel cell stack is heated using EMR.
  • the fuel cell or fuel cell stack may be heated using oven curing.
  • the laser beam may be expanded (for example, by the use of one or more mirrors) to create a heating zone with uniform power density.
  • each layer of the fuel cell may be cured by EMR separately.
  • a combination of fuel cell layers may be EMR cured separately, for example, a combination of the anode, the electrolyte, and the cathode layers.
  • a first fuel cell is EMR cured, assembled with a second fuel cell, and then the second fuel cell is EMR cured.
  • a first fuel cell is assembled with a second fuel cell, and then the first fuel cell and the second fuel cell are EMR cured separately.
  • a first fuel cell is assembled with a second fuel cell to form a fuel cell stack, and then the fuel cell stack is EMR cured.
  • a fuel cell stack comprising two or more fuel cells may be EMR cured. The sequence of laser heating/curing and assembling is applicable to all other heating methods.
  • an AMM produces each layer of a multiplicity of fuel cells simultaneously.
  • the AMM assembles each layer of a multiplicity of fuel cells simultaneously.
  • heating each layer or heating a combination of layers of a multiplicity of fuel cells takes place simultaneously. All the discussion and all the features described herein for a fuel cell or a fuel cell stack are applicable to the production, assembling and heating of the multiplicity of fuel cells.
  • a multiplicity of fuel cells may be 2 or more 20 or more, 50 or more, 80 or more, 100 or more, 500 or more, 800 or more, 1000 or more, 5000 or more or 10,000 or more.
  • a preferred treatment process is sintering.
  • the treatment process comprises exposing a substrate to a source of electromagnetic radiation (EMR).
  • EMR electromagnetic radiation
  • the EMR is exposed to a substrate having a first material.
  • the EMR has a peak wavelength ranging from 10 to 1500 nm.
  • the EMR has a minimum energy density of 0.1 Joule/cm 2 .
  • the EMR has a burst frequency of 10 4 -1000 Hz or 1-1000 Hz or 10-1000 Hz.
  • the EMR has an exposure distance of no greater than 50 mm.
  • the EMR has an exposure duration no less than 0.1 ms or 1 ms.
  • the EMR is applied with a capacitor voltage of no less than 100V.
  • a single pulse of EMR is applied with an exposure distance of about 10 mm and an exposure duration of 5-20 ms.
  • multiple pulses of EMR are applied at a burst frequency of 100Hz with an exposure distance of about 10 mm and an exposure duration of 5-20 ms.
  • the EMR consists of one exposure.
  • the EMR comprises no greater than 10 exposures, or no greater than 100 exposures, or no greater than 1000 exposures, or no greater than 10,000 exposures.
  • metals and ceramics are sintered almost instantaneously (milliseconds for «10 microns) using pulsed light.
  • the sintering temperature may be controlled to be in the range of 100 °C to 2000 °C.
  • the sintering temperature may be tailored as a function of depth.
  • the surface temperature is 1000 °C and the sub-surface is kept at 100 °C, wherein the sub-surface is 100 microns below the surface.
  • the material suitable for this treatment process includes yttria-stabilized zirconia (YSZ), 8YSZ (8mol% YSZ powder), yttirum, zirconium, gadolinia-doped ceria (GDC or CGO), samaria-doped ceria (SDC), scandia-stabilized zirconia (SSZ), lanthanum strontium manganite (LSM), lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel, NiO, NiO-YSZ, Cu-CGO, CU2O, CuO, cerium, copper, silver, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof.
  • YSZ yttria-stabilized zirconia
  • 8YSZ
  • This treatment process is applicable in the manufacturing process of a fuel cell.
  • a layer in a fuel cell i.e., anode, cathode, electrolyte, seal, catalyst, etc
  • a portion of a layer in a fuel cell is treated using processes described herein to be heated, cured, sintered, sealed, alloyed, foamed, evaporated, restructured, dried, annealed, or combinations thereof.
  • a combination of layers of a fuel cell are treated using processes described herein to be heated, cured, sintered, sealed, alloyed, foamed, evaporated, restructured, dried, annealed or combinations thereof, wherein the layers may be a complete layer or a partial layer.
  • the treatment process of this disclosure is preferably rapid, with the treatment duration varied from microseconds to milliseconds. The treatment duration may be accurately controlled.
  • the treatment process of this disclosure may produce fuel cell layers that have no cracks or have minimal cracking.
  • the treatment process of this disclosure controls the power density or energy density in the treatment volume (the volume of an object being treated) of the material being treated. The treatment volume may be accurately controlled.
  • the treatment process of this disclosure provides the same energy density or different energy densities in a treatment volume. In an embodiment, the treatment process of this disclosure provides the same treatment duration or different treatment durations in a treatment volume. In an embodiment, the treatment process of this disclosure provides simultaneous treatment for one or more treatment volumes. In an embodiment, the treatment process of this disclosure provides simultaneous treatment for one or more fuel cell layers or partial layers or combination of layers. In an embodiment, the treatment volume is varied by changing the treatment depth.
  • a first portion of a treatment volume is treated by electromagnetic radiation of a first wavelength; a second portion of the treatment volume is treated by electromagnetic radiation of a second wavelength.
  • the first wavelength is the same as the second wavelength.
  • the first wavelength is different from the second wavelength.
  • the first portion of a treatment volume has a different energy density from the second portion of the treatment volume.
  • the first portion of a treatment volume has a different treatment duration from the second portion of the treatment volume.
  • the EMR has a broad emission spectrum so that the desired effects are achieved for a wide range of materials having different absorption characteristics.
  • absorption of electromagnetic radiation refers to the process, wherein the energy of a photon is taken up by matter, such as the electrons of an atom.
  • the electromagnetic energy is transformed into internal energy of the absorber, for example, thermal energy.
  • the EMR spectrum extends from the deep ultraviolet (UV) range to the near infrared (IR) range, with peak pulse powers at 220 nm wavelength.
  • the power of such EMR is on the order of Megawatts.
  • Such EMR sources perform tasks such as breaking chemical bonds, sintering, ablating or sterilizing.
  • the EMR has an energy density of no less than 0.1, 1, or 10
  • the EMR has a power output of no less than 1 watt (W), 10 W, 100 W, 1000 W.
  • the EMR delivers power to the substrate of no less than 1 W, 10 W, 100 W, 1000 W.
  • such EMR exposure heats the material in the substrate.
  • the EMR has a range or a spectrum of different wavelengths.
  • the treated substrate is at least a portion of an anode, cathode, electrolyte, catalyst, barrier layer, or interconnect of a fuel cell.
  • the peak wavelength of the EMR is between 50 and 550 nm or between 100 and 300 nm.
  • the absorption of at least a portion of the substrate for at least one frequency of the EMR between 10 and 1500 nm is no less than 30% or no less than 50%.
  • the absorption of at least a portion of the substrate for at least one frequency between 50 and 550 nm is no less than 30% or no less than 50%.
  • the absorption of at least a portion of the substrate for at least one frequency between 100 and 300 nm is no less than 30% or no less than 50%.
  • Sintering is the process of compacting and forming a solid mass of material by heat or pressure without melting it to the point of liquefaction.
  • the substrate under EMR exposure is sintered but not melted.
  • the EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser, electron beam, microwave.
  • the substrate is exposed to the EMR for no less than 1 microsecond, no less than 1 millisecond.
  • the substrate is exposed to the EMR for less than 1 second at a time or less than 10 seconds at a time.
  • the substrate is exposed to the EMR for less than 1 second or less than 10 seconds.
  • the substrate is exposed to the EMR repeatedly, for example, more than 1 time, more than 3 times, more than 10 times.
  • the substrate is distanced from the source of the EMR for less than 50 cm, less than 10 cm, less than 1 cm, or less than 1 mm.
  • a second material is added to or placed on to the first material.
  • the second material is the same as the first material.
  • the second material may be exposed to EMR.
  • a third material may be added. The third material is exposed to EMR.
  • the first material comprises YSZ, 8YSZ, yttirum, zirconium, GDC, SDC, LSM, LSCF, LSC, nickel, NiO or cerium or a combination thereof.
  • the second material may comprise graphite.
  • the electrolyte, anode, or cathode comprises a second material.
  • the volume fraction of the second material in the electrolyte, anode, or cathode is less than 20%, 10%, 3%, or 1%.
  • the absorption rate of the second material for at least one frequency is greater than 30% or greater than 50%.
  • one or a combination of parameters may be controlled, wherein such parameters include distance between the EMR source and the substrate, the energy density of the EMR, the spectrum of the EMR, the voltage of the EMR, the duration of exposure, the burst frequency and the number of EMR exposures. Preferably, these parameters are controlled to minimize the formation of cracks in the substrate.
  • the EMR energy is delivered to a surface area of no less than 1 mm 2 , or no less than 1 cm 2 , or no less than 10 cm 2 , or no less than 100 cm 2 .
  • at least a portion of an adjacent material is heated at least in part by conduction of heat from the first material.
  • the layers of the fuel cell e.g., anode, cathode, electrolyte
  • they are no greater than 30 microns, no greater than 10 microns, or no greater than 1 micron.
  • the first material of the substrate is in the form of a powder, sol gel, colloidal suspension, hybrid solution or sintered material.
  • the second material may be added by vapor deposition.
  • the second material coats the first material.
  • the second material reacts with light, (e.g. focused light), as by a laser, and sintered or annealed with the first material.
  • the preferred treatment process of this disclosure enables rapid manufacturing of fuel cells by eliminating traditional, costly, time consuming, expensive sintering processes and replacing them with rapid, in situ methods that allow continuous manufacturing of the layers of a fuel cell in a single machine if desired. This process also shortens sintering time from hours and days to seconds or milliseconds or even microseconds.
  • this treatment method is used in combination with
  • This preferred treatment method enables tailored and controlled heating by tuning EMR characteristics (such as, wavelengths, energy density, burst frequency, and exposure duration) combined with controlling thicknesses of the layers of the substrate and heat conduction into adjacent layers to allow each layer to sinter, anneal, or cure at each desired target
  • This process enables more uniform energy applications, decreases or eliminates cracking, which improves electrolyte performance.
  • the substrate treated with this preferred process also has less thermal stress due to more uniform heating.
  • such particle size distribution comprises DIO and D90, wherein 10% of the particles have a diameter no greater than D10 and 90% of the particles have a diameter no greater than D90, wherein D90/D10 is in the range of from 1.5 to 100.
  • such particle size distribution is bimodal such that the average particle size in the first mode is at least 5 times the average particle size in the second mode.
  • such particle size distribution comprises D50, wherein 50% of the particles have a diameter no greater than D50, wherein D50 is no greater than 100 nm.
  • the sintering processes utilize electromagnetic radiation (EMR), or plasma, or a furnace, or hot fluid, or a heating element, or combinations thereof.
  • EMR electromagnetic radiation
  • an EMR source just sufficient enough to sinter a material has power capacity P.
  • the material is sintered with EMR sources having much less power capacity, e.g., 50% P or less, 40% P or less, 30% P or less, 20% P or less, 10% P or less, 5% P or less.
  • a method of sintering a material comprising mixing particles with a liquid to form a dispersion, wherein the particles have a particle size distribution comprising D10 and D90, wherein 10% of the particles have a diameter no greater than D10 and 90% of the particles have a diameter no greater than D90, wherein D90/D10 is in the range of from 1.5 to 100; depositing the dispersion on a substrate to form a layer; and treating the layer to cause at least a portion of the particles to sinter.
  • the particle size distribution is a number distribution determined by dynamic light scattering.
  • Dynamic light scattering is a technique that can be used to determine the size distribution profile of small particles in a dispersion or suspension.
  • temporal fluctuations are typically analyzed by means of the intensity or photon auto-correlation function (also known as photon correlation spectroscopy or quasi-elastic light scattering).
  • the autocorrelation function (ACF) usually decays starting from zero delay time, and faster dynamics due to smaller particles lead to faster decorrelation of scattered intensity trace. It has been shown that the intensity ACF is the Fourier transformation of the power spectrum, and therefore the DLS measurements can be equally well performed in the spectral domain.
  • the particle size distribution is determined by transmission electron microscopy (TEM).
  • TEM is a microscopy technique in which a beam of electrons is transmitted through a specimen to form an image.
  • the specimen is most often a suspension on a grid.
  • An image is formed from the interaction of the electrons with the sample as the beam is transmitted through the specimen.
  • the image is then magnified and focused onto an imaging device, such as a fluorescent screen or a sensor such as a scintillator attached to a charge- coupled device.
  • a method of sintering a material comprising mixing particles with a liquid to form a dispersion, wherein the particles have a particle size distribution comprising D50, wherein 50% of the particles have a diameter no greater than D50, wherein D50 is no greater than 100 nm; depositing the dispersion on a substrate to form a layer; and treating the layer to cause at least a portion of the particles to sinter.
  • D50 is no greater than 50 nm, or no greater than 30 nm, or no greater than 20 nm, or no greater than 10 nm, or no greater than 5 nm.
  • the layer has a thickness of no greater than 1 mm or no greater than 500 microns or no greater than 300 microns or no greater than 100 microns or no greater than 50 microns.
  • depositing comprises material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing, vat photopolymerization, powder bed fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing, or combinations thereof.
  • said liquid comprises water and at least one organic solvent having a lower boiling point than water and miscible with water.
  • said liquid comprises water, a surfactant, a dispersant and no polymeric binder.
  • said liquid comprises one or more organic solvents and no water.
  • the particles comprise Cu, CuO, CU2O, Ag, Ag 2 0, Au, AU2O, AU2O3, titanium, yttria-stabilized zirconia (YSZ), 8YSZ (8mol% YSZ powder), yttirum, zirconium, gadolinia-doped ceria (GDC or CGO), samaria-doped ceria (SDC), scandia-stabilized zirconia (SSZ), lanthanum strontium manganite (LSM), lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel (Ni), NiO, NiO- YSZ, Cu-CGO, cerium, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof.
  • YSZ y
  • D10 is in the range of from 5 nm to 50 nm or from 5 nm to 100 nm or from 5 nm to 200 nm.
  • D90 is in the range of from 50 nm to 500 nm or from 50 nm to 1000 nm.
  • D90/D10 is in the range of from 2 to 100 or from 4 to 100 or from 2 to 20 or from 2 to 10 or from 4 to 20 or from 4 to 10.
  • the method comprises drying the dispersion after depositing.
  • drying comprises heating the dispersion before deposition, heating the substrate that is contact with the dispersion, or combination thereof. Drying may take place for a time period in the range of 1 ms to 1 min or 1 s to 30 s or 3 s to 10 s. In some embodiments, the dispersion may be deposited at a temperature in the range of 40°C to 100°C or 50°C to 90°C or 60°C to 80°C or about 70°C.
  • treating comprises the use of electromagnetic radiation (EMR), or a furnace, or plasma, or hot fluid, or a heating element, or combinations thereof.
  • EMR electromagnetic radiation
  • the EMR comprises UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser, electron beam or microwave or a combination thereof.
  • the EMR consists of one exposure.
  • the EMR has an exposure frequency of 10 4 -1000 Hz or 1-1000 Hz or 10-1000 Hz.
  • the EMR has an exposure distance of no greater than 50 mm.
  • the EMR has an exposure duration no less than 0.1 ms or 1 ms.
  • the EMR is applied with a capacitor voltage of no less than 100V.
  • a fuel cell is an electrochemical apparatus that converts the chemical energy from a fuel into electricity through an electrochemical reaction.
  • fuel cells e.g., proton-exchange membrane fuel cells (PEMFCs), solid oxide fuel cells (SOFCs).
  • a fuel cell typically comprises an anode, a cathode, an electrolyte, an interconnect, optionally a barrier layer and/or optionally a catalyst. Both the anode and the cathode are electrodes.
  • the listings of material for the electrodes, the electrolyte, and the interconnect in a fuel cell are applicable in some cases to the EC gas producer and the EC compressor. These listings are only examples and not limiting.
  • Figs. 1-5 illustrate various embodiments of the components in a fuel cell or a fuel cell stack.
  • the anode, cathode, electrolyte, and interconnect are cuboids or rectangular prisms.
  • Fig. 1 illustrates a fuel cell component comprising an anode, an electrolyte and a cathode.
  • the top layer in Fig. is an anode layer 101, the top layer is the cathode 102 and the middle layer is an electrolyte 103.
  • Fig. 2 illustrates a fuel cell component comprising an anode, an electrolyte, a barrier layer and a cathode.
  • the top layer is an anode 201
  • bottom layer 202 is a cathode
  • layer 203 is the electrolyte
  • layers 204 are barrier layers.
  • Fig. 3 illustrates a fuel cell component comprising an anode, a catalyst, an electrolyte, a barrier layer and a cathode.
  • Layer 301 schematically illustrates the anode
  • layer 302 is the cathode
  • layer 303 is an electrolyte
  • layers 304 are barrier layers
  • layer 305 is a catalyst.
  • Fig. 4 illustrates a fuel cell component comprising an anode, a catalyst, an electrolyte, a barrier layer, a cathode and an interconnect.
  • Layer 401 schematically illustrates an anode
  • layer 402 represents a cathode
  • layer 403 represents an electrolyte
  • layers 404 represents barrier layers
  • layer 405 represents a catalyst
  • layer 406 represents an interconnect.
  • Fig. 5 schematically illustrates two fuel cells in a fuel cell stack.
  • the two fuel cells are denoted "Fuel Cell 1" and "Fuel Cell 2".
  • Each fuel cell in Fig. 5 comprises an anode layer 501, cathode layer 502, electrolyte layer 503, barrier layers 504, catalyst layer 505 and interconnect layer 506.
  • Two fuel cell repeat units or two fuel cells form a stack as illustrated. As is seen, on one side interconnect 506 is in contact with the largest surface of cathode 502 of fuel cell 2 (or fuel cell repeat unit) and on the opposite side interconnect 506 is in contact with the largest surface of catalyst 505 (optional) or the anode 501 of bottom fuel cell 2 (or fuel cell repeat unit).
  • the cathode comprises perovskites, such as LSC, LSCF or LSM. In some embodiments, the cathode comprises one or more of lanthanum, cobalt, strontium or manganite. In an embodiment, the cathode is porous. In some embodiments, the cathode comprises one or more of YSZ, nitrogen, nitrogen boron doped graphene,
  • the cathode comprises LSCo, LCo, LSF, LSCoF, or a combination thereof. In some embodiments, the cathode comprises perovskites LaCo03, LaFe03, LaMn03,
  • the cathode comprises a material selected from the group consisting of lanthanum strontium manganite, lanthanum strontium ferrite, and lanthanum strontium cobalt ferrite. In preferred embodiments, the cathode comprises lanthanum strontium manganite.
  • the anode comprises copper, nickle-oxide, nickle-oxide-YSZ, NiO- GDC, NiO-SDC, aluminum doped zinc oxide, molybdenum oxide, lanthanum, strontium, chromite, ceria, perovskites (such as, LSCF [La ⁇ l-x ⁇ Sr ⁇ x ⁇ Co ⁇ l-y ⁇ Fe ⁇ y ⁇ C>3] or LSM [La ⁇ l- x ⁇ Sr ⁇ x ⁇ MnC>3], where x is usually in the range of 0.15-0.2 and y is in the range of 0.7 to 0.8).
  • LSCF La ⁇ l-x ⁇ Sr ⁇ x ⁇ Co ⁇ l-y ⁇ Fe ⁇ y ⁇ C>3
  • LSM La ⁇ l- x ⁇ Sr ⁇ x ⁇ MnC>3
  • the anode comprises SDC or BZCYYb coating or barrier layer to reduce coking and sulfur poisoning. In an embodiment, the anode is porous. In some embodiments, the anode comprises a combination of electrolyte material and electrochemically active material or a combination of electrolyte material and electrically conductive material.
  • the anode comprises nickel and yttria stabilized zirconia. In a preferred embodiment, the anode is formed by reduction of a material comprising nickel oxide and yttria stabilized zirconia. In a preferred embodiment, the anode comprises nickel and gadolinium stabilized ceria. In a preferred embodiment, the anode is formed by reduction of a material comprising nickel oxide and gadolinium stabilized ceria.
  • the electrolyte in a fuel cell comprises stabilized zirconia (e.g., YSZ, YSZ-8, Yo.i 6 Zro. 84 O 2 ).
  • the electrolyte comprises doped LaGa03, (e.g., LSGM, Lao. 9 Sro. 1 Gao. 8 MgO.2O 3 ).
  • the electrolyte comprises doped ceria, (e.g., GDC, Gdo. 2 Ceo. 8 O 2 ).
  • the electrolyte comprises stabilized bismuth oxide (e.g., BVCO, Bi2Vo.9Cuo.1O5.35).
  • the electrolyte comprises zirconium oxide, yttria stabilized zirconium oxide (also known as YSZ, YSZ8 (8mole% YSZ)), ceria, gadolinia, scandia, magnesia or calcia or a combination thereof.
  • the electrolyte is sufficiently impermeable to prevent significant gas transport and prevent significant electrical conduction; and allow ion conductivity.
  • the electrolyte comprises doped oxide such as cerium oxide, yttrium oxide, bismuth oxide, lead oxide, lanthanum oxide.
  • the electrolyte comprises perovskite, such as, LaCoFeC>3 or LaCoC>3 or Ceo.9Gdo.1O2 (GDC) or Ceo.9Smo.1O2 (SDC, samaria doped ceria) or scandia stabilized zirconia or a combination thereof.
  • perovskite such as, LaCoFeC>3 or LaCoC>3 or Ceo.9Gdo.1O2 (GDC) or Ceo.9Smo.1O2 (SDC, samaria doped ceria) or scandia stabilized zirconia or a combination thereof.
  • the electrolyte comprises a material selected from the group consisting of zirconia, ceria, and gallia.
  • the material is stabilized with a stabilizing material selected from the group consisting of scandium, samarium, gadolinium, and yttrium.
  • the material comprises yttria stabilized zirconia.
  • the interconnect comprises silver, gold, platinum, AISI441, ferritic stainless steel, stainless steel, lanthanum, chromium, chromium oxide, chromite, cobalt, cesium, Cr2C>3, or a combination thereof.
  • the anode comprises a LaCrC>3 coating on Cr2C>3 or NiCo2C>4 or MnCo2C>4 coatings.
  • the interconnect surface is coated with Cobalt and/or Cesium.
  • the interconnect comprises ceramics.
  • the interconnect comprises lanthanum chromite or doped lanthanum chromite.
  • the interconnect comprises a material further comprising metal, stainless steel, ferritic steel, crofer, lanthanum chromite, silver, metal alloys, nickel, nickel oxide, ceramics, or graphene or a combination thereof.
  • the fuel cell comprises a catalyst, such as, platinum, palladium, scandia, chromium, cobalt, cesium, Ce02, nickle, nickle oxide, zine, copper, titantia, ruthenium, rhodiu, MoS2, molybdenum, rhenium, vandia, manganese, magnesium or iron or a combination thereof.
  • the catalyst promotes methane reforming reactions to generate hydrogen and carbon monoxide such that they may be oxidized in the fuel cell.
  • the catalyst is part of the anode, especially nickel anode which has inherent methane reforming properties.
  • the catalyst is between l%-5%, or 0.1% to 10% by mass.
  • the catalyst is used on the anode surface or in the anode.
  • such anode catalysts reduce harmful coking reactions and carbon deposits.
  • simple oxide versions of catalysts or perovskite may be used as catalysts.
  • about 2% mass CeC>2 catalyst is used for methane-powered fuel cells.
  • the catalyst may be dipped or coated on the anode.
  • the catalyst is made by an additive manufacturing machine (AMM) and incorporated into the fuel cell using the AMM.
  • AMM additive manufacturing machine
  • the unique manufacturing methods discussed herein have described the assembly of ultra-thin fuel cells and fuel cell stacks.
  • the fuel cell has at least one thick layer per repeat unit. This may be the anode (such as an anode-supported fuel cell) or the interconnect (such as an interconnect-supported fuel cell).
  • pressing or compression steps are typically necessary to assemble the fuel cell components to achieve gas tightness and/or proper electrical contact in traditional
  • the thick layers are necessary not only because traditional methods (like tape casting) cannot produce ultra-thin layers but also because the layers must be thick to endure the pressing or compression steps.
  • the preferred manufacturing methods of this disclosure have eliminated the need for pressing or compression.
  • manufacturing methods of this disclosure have also enabled the making of ultra-thin layers.
  • the multiplicity of the layers in a fuel cell or a fuel cell stack provides sufficient structural integrity for proper operation when they are made according to this disclosure.
  • a fuel cell comprising an anode no greater than 1 mm or 500 microns or 300 microns or 100 microns or 50 microns or no greater than 25 microns in thickness.
  • the cathode no greater than 1 mm or 500 microns or 300 microns or 100 microns or 50 microns or no greater than 25 microns in thickness.
  • the electrolyte no greater than 1 mm or 500 microns or 300 microns or 100 microns or 50 microns or 30 microns in thickness.
  • the fuel cell comprises an interconnect having a thickness of no less than 50 microns.
  • a fuel cell comprises an anode no greater than 25 microns in thickness, a cathode no greater than 25 microns in thickness, and an electrolyte no greater than 10 microns or 5 microns in thickness.
  • the fuel cell comprises an interconnect having a thickness of no less than 50 microns.
  • the interconnect has a thickness in the range of 50 microns to 5 cm.
  • a fuel cell comprises an anode no greater than 100 microns in thickness, a cathode no greater than 100 microns in thickness, an electrolyte no greater than 20 microns in thickness, and an interconnect no greater than 30 microns in thickness.
  • a fuel cell comprises an anode no greater than 50 microns in thickness, a cathode no greater than 50 microns in thickness, an electrolyte no greater than 10 microns in thickness, and an interconnect no greater than 25 microns in thickness.
  • the interconnect has a thickness in the range of 1 micron to 20 microns.
  • the fuel cell comprises a barrier layer between the anode and the electrolyte, or a barrier layer between the cathode and the electrolyte, or both barrier layers.
  • the barrier layers are the interconnects. In such cases, the reactants are directly injected into the anode and the cathode.
  • the cathode has a thickness of no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns.
  • the anode has a thickness no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns.
  • the electrolyte has a thickness of no greater than 5 microns, or no greater than 2 microns, or no greater than 1 micron, or no greater than 0.5 micron.
  • the interconnect is made of a material comprising metal, stainless steel, silver, metal alloys, nickel, nickel oxide, ceramics, or graphene.
  • the fuel cell has a total thickness of no less than 1 micron.
  • each fuel cell comprises an anode no greater than 25 microns in thickness, a cathode no greater than 25 microns in thickness, an electrolyte no greater than 10 microns in thickness, and an interconnect having a thickness in the range from 100 nm to 100 microns.
  • each fuel cell comprises a barrier layer between the anode and the electrolyte, or a barrier layer between the cathode and the electrolyte, or both barrier layers.
  • the barrier layers are the interconnects.
  • the interconnect is made of silver.
  • the interconnect has a thickness in the range from 500 nm to 1000 nm.
  • the interconnect is made of a material comprising metal, stainless steel, silver, metal alloys, nickel, nickel oxide, ceramics, or graphene.
  • the cathode has a thickness of no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns.
  • the anode has a thickness of no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns.
  • the electrolyte has a thickness of no greater than 5 microns, or no greater than 2 microns, or no greater than 1 micron, or no greater than 0.5 micron.
  • each fuel cell has a total thickness of no less than 1 micron.
  • steps (a)-(c) are performed using additive manufacturing.
  • said additive manufacturing employs one or more of extrusion,
  • the method comprises assembling the anode, the cathode, and the electrolyte using additive manufacturing. In an embodiment, the method comprises forming an interconnect and assembling the interconnect with the anode, the cathode, and the electrolyte.
  • the method comprises making at least one barrier layer.
  • the at least one barrier layer is used between the electrolyte and the cathode or between the electrolyte and the anode, or both.
  • the at least one barrier layer also acts as an interconnect.
  • the method comprises heating the fuel cell such that shrinkage rates of the anode, the cathode, and the electrolyte are matched. In some embodiments, such heating takes place for no greater than 30 minutes, preferably no greater than 30 seconds, and most preferably no greater than 30 milliseconds. In this disclosure, matching shrinkage rates during heating is discussed in detail below (Matching SRTs).
  • a fuel cell comprises a first composition and a second composition, wherein the first composition has a first shrinkage rate and the second composition has a second shrinkage rate
  • the heating described in this disclosure preferably takes place such that the difference between the first shrinkage rate and the second shrinkage rate is no greater than 75% of the first shrinkage rate.
  • the heating employs electromagnetic radiation (EMR).
  • EMR electromagnetic radiation
  • EMR comprises UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser, electron beam.
  • heating is performed in situ.
  • Also disclosed herein is a method of making a fuel cell stack comprising a multiplicity of fuel cells, the method comprising: (a) forming an anode no greater than 25 microns in thickness in each fuel cell, (b) forming a cathode no greater than 25 microns in thickness in each fuel cell, (c) forming an electrolyte no greater than 10 microns in thickness in each fuel cell, and (d) producing an interconnect having a thickness of from 100 nm to 100 microns in each fuel cell.
  • steps (a)-(d) are performed using AM.
  • AM employs one or more of processes of extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition or lamination.
  • the method of making a fuel cell stack comprises assembling the anode, the cathode, the electrolyte, and the interconnect using AM.
  • the method comprises making at least one barrier layer in each fuel cell.
  • the at least one barrier layer is used between the electrolyte and the cathode or between the electrolyte and the anode or both.
  • the at least one barrier layer also acts as the interconnect.
  • the method of making a fuel cell stack comprises heating each fuel cell such that shrinkage rates of the anode, the cathode, and the electrolyte are matched. In an embodiment, such heating takes place for no greater than 30 minutes, or no greater than 30 seconds, or no greater than 30 milliseconds.
  • said heating comprises one or more of electromagnetic radiation (EMR).
  • EMR electromagnetic radiation
  • EMR comprises UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser, electron beam. In an embodiment, heating is performed in situ.
  • the method comprises heating the entire fuel cell stack such that shrinkage rates of the anode, the cathode, and the electrolyte are matched. In some embodiments, such heating takes place for no greater than 30 minutes, or no greater than 30 seconds, or no greater than 30 milliseconds.
  • an electrolyte comprising (a) formulating a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and a size distribution, and a solvent; (b) forming an electrolyte comprising the colloidal suspension; and (c) heating at least a portion of the electrolyte; wherein formulating the colloidal suspension is preferably optimized by controlling the pH of the colloidal suspension, or concentration of the binder in the colloidal suspension, or composition of the binder in the colloidal suspension, or the range of diameters of the particles, or maximum diameter of the particles, or median diameter of the particles, or the size distribution of the particles, or boiling point of the solvent, or surface tension of the solvent, or composition of the solvent, or thickness of the minimum dimension of the electrolyte, or the composition of the particles, or combinations thereof.
  • a method of making a fuel cell comprising (a) obtaining a cathode and an anode; (b) modifying the cathode surface and the anode surface; (c) formulating a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and a size distribution, and a solvent; (d) forming an electrolyte comprising the colloidal suspension between the modified anode surface and the modified cathode surface; and (e) heating at least a portion of the electrolyte; wherein formulating the colloidal suspension comprises controlling pH of the colloidal suspension, or concentration of the binder in the colloidal suspension, or composition of the binder in the colloidal suspension, or the range of diameters of the particles, or maximum diameter of the particles, or median diameter of the particles, or the size distribution of the particles, or boiling point of the solvent, or surface tension of the solvent, or composition of the solvent, or thickness of the minimum dimension of the electrolyte, or the composition of the particles,
  • the anode and the cathode are obtained via any suitable means.
  • the modified anode surface and the modified cathode surface have a maximum height profile roughness that is less than the average diameter of the particles in the colloidal suspension.
  • the maximum height profile roughness 900 refers to the maximum distance between any trough 902 and an adjacent peak 904 of an anode surface or a cathode surface as illustrated in Fig. 9.
  • the anode surface and the cathode surface are modified via any suitable means.
  • a method of making a fuel cell comprising (a) obtaining a cathode and an anode; (b) formulating a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and a size distribution, and a solvent; (c) forming an electrolyte comprising the colloidal suspension between the anode and the cathode; and (d) heating at least a portion of the electrolyte; wherein formulating the colloidal suspension comprises controlling pH of the colloidal suspension, or concentration of the binder in the colloidal suspension, or composition of the binder in the colloidal suspension, or the range of diameters of the particles, or maximum diameter of the particles, or median diameter of the particles, or the size distribution of the particles, or boiling point of the solvent, or surface tension of the solvent, or composition of the solvent, or thickness of the minimum dimension of the electrolyte, or the composition of the particles, or combinations thereof.
  • the anode and the cathode are obtained via any suitable means.
  • the anode surface in contact with the electrolyte and the cathode surface in contact with the electrolyte have a maximum height profile roughness that is less than the average diameter of the particles in the colloidal suspension.
  • the solvent comprises water.
  • the solvent comprises an organic component.
  • the solvent may comprise ethanol, butanol, alcohol, terpineol, diethyl ether 1,2-dimethoxyethane (DME (ethylene glycol dimethyl ether), 1- propanol (n-propanol, n-propyl alcohol), or butyl alcohol or a combination thereof.
  • DME diethyl ether 1,2-dimethoxyethane
  • the solvent surface tension is less than half of water's surface tension in air. In an embodiment, the solvent surface tension is less than 30 mN/m at atmospheric conditions.
  • the electrolyte is formed adjacent to a first substrate or the electrolyte is formed between a first substrate and a second substrate.
  • the first substrate has a maximum height profile roughness that is less than the average diameter of the particles.
  • the particles have a packing density greater than 40%, or greater than 50%, or greater than 60%. In an embodiment, the particles have a packing density close to the random close packing (RCP) density.
  • Random close packing is an empirical parameter used to characterize the maximum volume fraction of solid objects obtained when they are packed randomly.
  • a container is randomly filled with objects, and then the container is shaken or tapped until the objects do not compact any further, at this point the packing state is RCP.
  • the packing fraction is the volume taken by a number of particles in a given space of volume.
  • the packing fraction determines the packing density. For example, when a solid container is filled with grain, shaking the container will reduce the volume taken up by the objects, thus allowing more grain to be added to the container. Shaking increases the density of packed objects. When shaking no longer increases the packing density, a limit is reached and if this limit is reached without obvious packing into a regular crystal lattice, this is the empirical random close-packed density.
  • the median particle diameter is between 50 nm and 1000 nm, or between 100 nm and 500 nm, or approximately 200 nm.
  • the first substrate comprises particles having a median particle diameter, wherein the median particle diameter of the electrolyte may be no greater than 10 times and no less than 1/10 of the median particle diameter of the first substrate.
  • the first substrate comprises a particle size distribution that is bimodal having a first mode and a second mode, each having a median particle diameter.
  • the median particle diameter in the first mode of the first substrate is greater than 2 times, or greater than 5 times, or greater than 10 times that of the second mode.
  • the particle size distribution of the first substrate may be adjusted to change the behavior of the first substrate during heating.
  • the first substrate has a shrinkage that is a function of heating
  • the particles in the colloidal suspension may have a maximum particle diameter and a minimum particle diameter, wherein the maximum particle diameter is less than 2 times, or less than 3 times, or less than 5 times, or less than 10 times the minimum particle diameter.
  • the minimum dimension of the electrolyte is less than 10 microns, or less than 2 microns, or less than 1 micron, or less than 500 nm.
  • the electrolyte has a gas permeability of no greater than 1 millidarcy, preferably no greater than 100 microdarcy, and most preferably no greater than 1 microdarcy. Preferably, the electrolyte has no cracks penetrating through the minimum dimension of the electrolyte.
  • the boiling point of the solvent is no less than 200 °C, or no less than 100 °C, or no less than 75°C. In some embodiments, the boiling point of the solvent is no greater than 125 °C, or no greater than 100 °C, or no greater than 85 °C, no greater than 70 °C.
  • the pH of the colloidal suspension is no less than 7, or no less than 9, or no less than 10.
  • the additive comprises polyethylene glycol (PEG), ethyl cellulose, polyvinylpyrrolidone (PVP), polyvinyl butyral (PVB), butyl benzyl phthalate (BBP), polyalkalyne glycol (PAG) or a combination thereof.
  • the additive concentration is no greater than 100 mg/cm3, or no greater than 50 mg/cm3, or no greater than 30 mg/cm3, or no greater than 25 mg/cm3.
  • the colloidal suspension is milled.
  • the colloidal suspension is milled using a rotational mill wherein the rotational mill is operated at no less than 20 rpm, or no less than 50 rpm, or no less than 100 rpm, or no less than 150 rpm.
  • the colloidal suspension is milled using zirconia milling balls or tungsten carbide balls wherein the colloidal suspension is milled for no less than 2 hours, or no less than 4 hours, or no less than 1 day, or no less than 10 days.
  • the particle concentration in the colloidal suspension is no greater than 30 wt%, or no greater than 20 wt%, or no greater than 10 wt%. In other embodiments, the particle concentration in the colloidal suspension is no less than 2 wt%. In some embodiments, the particle concentration in the colloidal suspension is no greater than 10 vol%, or no greater than 5 vol%, or no greater than 3 vol%, or no greater than 1 vol%. In an embodiment, the particle concentration in the colloidal suspension is no less than 0.1 vol%.
  • the electrolyte is formed using an additive manufacturing machine (AMM).
  • the first substrate is formed using an AMM.
  • the heating comprises the use of electromagnetic radiation (EMR) wherein the EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light or laser.
  • EMR electromagnetic radiation
  • the first substrate and the electrolyte are heated to cause co-sintering.
  • the first substrate, the second substrate, and the electrolyte are heated to cause co-sintering.
  • the EMR is controlled to preferentially sinter the first substrate over the electrolyte.
  • the electrolyte is compresses after heating.
  • the first substrate and the second substrate apply compressive stress to the electrolyte after heating.
  • the first substrate and the second substrate that are applying compressive stress are the anode and cathode of a fuel cell.
  • the minimum dimension of the electrolyte is between 500 nm and 5 microns or between 1 micron and 2 microns.
  • SOFCs solid oxide fuel cells
  • the fuel cell stack is configured to be made into a cartridge form, such as an easily detachable flanged fuel cell cartridge (FCC) design.
  • Fig. 11A illustrates a perspective view of a fuel cell cartridge (FCC).
  • FCC 1110 comprises holes for bolts 1111, cathode layer 1112, barrier layer 1113, anode layer 1114, gas channels 1115 in the electrodes (anode and cathode), electrolyte layer 1117.
  • an air heat exchanger 1116, fuel heat exchanger 1118 and top interconnect 1136 Air heat exchanger 1116 and fuel heat exchanger 1118 combined form an integrated multi-fluid heat exchanger.
  • FIG. llC illustrates top view and bottom view of a fuel cell cartridge (FCC).
  • FCC 1110 comprises holes for bolts 1111, air inlet 1131, air outlet 1132, fuel inlet 1133, fuel outlet 1134, bottom 1135 and top interconnect 1136 of FCC 1110.
  • Fig. 11C further illustrates the top view and bottom view of an embodiment of FCC 1110, in which the length of the oxidant side of FCC 1110 is shown L, the length of the fuel side of FCC 1110 is shown L f , the width of the oxidant (air inlet 1131) entrance is shown W 0 , and the width of the fuel inlet 1133 is shown W f .
  • L the length of the oxidant side of FCC 1110
  • L f the length of the fuel side of FCC 1110
  • W 0 the width of the oxidant (air inlet 1131) entrance
  • W f the width of the fuel inlet 1133
  • bottom 1135 is an interconnect and 1131, 1132, 1133, 1134 are openings for fluid passage, e.g., in the direction perpendicular to the lateral direction.
  • FIG. 11B illustrates cross-sectional views of a fuel cell cartridge (FCC).
  • the 11B comprises electrical bolt isolation 1121, anode 1114, seal 1123 that seals anode 1114 from air flow, cathode 1112 and seal 1124 that seals cathode 1112 from fuel flow.
  • the bolts may be isolated electrically with a seal as well.
  • the seals may be dual functional seal (DFS) comprising YSZ (yttria-stabilized zirconia) or a mixture of 3YSZ (3 mol%
  • the DFS is impermeable to non-ionic substances and electrically insulating.
  • the mass ratio of 3YSZ/8YSZ is in the range of from 10/90 to 90/10. In some embodiments, the mass ratio of 3YSZ/8YSZ is about 50/50. In some embodiments, the mass ratio of 3YSZ/8YSZ is 100/0 or 0/100.
  • a fuel cell cartridge comprising an anode, a cathode, an electrolyte, an interconnect, a fuel entrance on a fuel side of the FCC, an oxidant entrance on an oxidant side of the FCC, at least one fluid exit, wherein the fuel entrance has a width of W f , the fuel side of the FCC has a length of L f , the oxidant entrance has a width of W 0 , the oxidant side of the FCC has a length of L 0 , wherein W f /L f is in the range of 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 0.9, or 0.5 to 1.0 and W 0 /L 0 is in the range of 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 0.9, or 0.5 to 1.0.
  • W 0 /L 0 is in the range of 0.1 to 1.0, or 0.1 to 0.9
  • the air and fuel entrances and exits are on one surface of the FCC wherein the FCC comprises no protruding fluid passages on said surface.
  • the surface is smooth with a maximum elevation change of no greater than 1 mm, or no greater than 100 microns, or no greater than 10 microns.
  • an FCC comprises a barrier layer between the electrolyte and the cathode, or between the electrolyte and the anode, or both.
  • the FCC comprises a dual functional seal (DFS) that is impermeable to non-ionic substances and electrically insulating.
  • the DFS comprises YSZ (yttria-stabilized zirconia) or a mixture of 3YSZ (3 mol% Y2O3 in ZrCh) and 8YSZ (8 mol% Y2O3 in ZrCh).
  • the interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid dispersing components. In some embodiments, the interconnect comprises no fluid dispersing element while the anode and cathode comprise fluid channels.
  • the FCC is detachably fixed to a mating surface and not soldered nor welded to the mating surface.
  • the FCC may be bolted to or pressed to the mating surface.
  • the mating surface comprises a matching fuel entrance, matching oxidant entrance, and at least one matching fluid exit.
  • a fuel cell cartridge comprising an anode, a cathode, an electrolyte, an interconnect, a fuel entrance, an oxidant entrance, at least one fluid exit, wherein said entrances and exit are on one surface of the FCC and said FCC comprises no protruding fluid passage on the surface.
  • the surface may be smooth with a maximum elevation change of no greater than 1 mm, or no greater than 100 microns, or no greater than 10 microns.
  • the FCC comprises a DFS that is impermeable to non-ionic substances and electrically insulating.
  • said interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid dispersing components.
  • said interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid channels.
  • the FCC is detachably fixed to a mating surface and not soldered nor welded to said mating surface.
  • the FCC is bolted to or pressed to the mating surface.
  • the mating surface comprises matching fuel entrance, matching oxidant entrance, and at least one matching fluid exit.
  • FCC fuel cell cartridge
  • the FCC comprises an anode, a cathode, an electrolyte, an
  • a fuel entrance on a fuel side of the FCC an oxidant entrance on an oxidant side of the FCC, at least one fluid exit
  • the fuel entrance has a width of W f
  • the fuel side of the FCC has a length of L f
  • the oxidant entrance has a width of W 0
  • the oxidant side of the FCC has a length of L 0
  • W f /L f is in the range of 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 0.9, or 0.5 to 1.0
  • W 0 /L 0 is in the range of 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 0.9, or 0.5 to 1.0
  • the FCC is detachably fixed to the mating surface.
  • the FCC is not soldered nor welded to said mating surface. In some embodiments, the FCC is bolted to or pressed to said mating surface. In other embodiments, said mating surface comprises matching fuel entrance, matching oxidant entrance, and at least one matching fluid exit. [218] In some embodiments, said entrances and exits are on one surface of the FCC and wherein the FCC comprises no protruding fluid passage on said surface. The surface may be smooth with a maximum elevation change of no greater than 1 mm, or no greater than 100 microns, or no greater than 10 microns.
  • said interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid dispersing components.
  • said anode and cathode comprise fluid dispersing components.
  • interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid channels.
  • a method comprising pressing or bolting together a fuel cell cartridge (FCC) and a mating surface the method excludes welding or soldering together the FCC and the mating surface, wherein the FCC comprises an anode, a cathode, an electrolyte, an interconnect, a fuel entrance on a fuel side of the FCC, an oxidant entrance on an oxidant side of the FCC, at least one fluid exit, wherein the fuel entrance has a width of W f , the fuel side of the FCC has a length of L f , the oxidant entrance has a width of W 0 , the oxidant side of the FCC has a length of L 0 , wherein W f /L f is in the range of 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 0.9, or 0.5 to 1.0 and W 0 /L 0 is in the range of 0.1 to 1.0, or 0.1
  • said entrances and exit are on one surface of the FCC wherein the FCC comprises no protruding fluid passage on said surface.
  • the surface is smooth with a maximum elevation change of no greater than 1 mm, or no greater than 100 microns, or no greater than 10 microns.
  • said interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid dispersing components.
  • said interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid channels.
  • a fuel cell cartridge comprising a fuel cell and a fuel cell casing, wherein the fuel cell comprises an anode, a cathode and an electrolyte, wherein at least a portion of the fuel cell casing is made of the same material as the electrolyte.
  • the electrolyte is in contact with the portion of the fuel cell casing made of the same material.
  • the electrolyte and the portion of the fuel cell casing are made of a DFS, wherein the DFS comprises 3YSZ (3 mol% Y2O3 in ZrCh) and 8YSZ (8 mol% Y2O3 in ZrCh), wherein the mass ratio of 3YSZ/8YSZ is in the range of from 100/0 to 0/100 or from 10/90 to 90/10 and wherein the DFS is impermeable to non-ionic substances and electrically insulating.
  • the mass ratio of 3YSZ/8YSZ is about 50/50 or 40/60 or 60/40 or 30/70 or 70/30 or 20/80 or 80/20.
  • said fuel cell casing comprises a fuel entrance and fuel passage for the anode, an oxidant entrance and oxidant passage for the cathode, and at least one fluid exit.
  • said entrances and at least one exit are on one surface of the FCC wherein the FCC comprises no protruding fluid passage on said surface.
  • the fuel cell casing is in contact with at least a portion of the anode.
  • the FCC comprises a barrier layer between the electrolyte and the cathode and between the fuel cell casing and the cathode.
  • the FCC comprises an interconnect, wherein the interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid dispersing components.
  • the FCC comprises an interconnect, wherein the interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid channels.
  • the FCC is detachably fixed to a mating surface and not soldered nor welded to said mating surface.
  • said mating surface comprises matching fuel entrance, matching oxidant entrance, and at least one matching fluid exit.
  • a DFS comprising 3YSZ (3 mol% Y203 in Zr02) and 8YSZ (8 mol% Y 2 O 3 in ZrCh), wherein the mass ratio of 3YSZ/8YSZ is in the range of from 10/90 to 90/10 and wherein the DFS is impermeable to non-ionic substances and electrically insulating.
  • the mass ratio of 3YSZ/8YSZ is about 50/50 or 40/60 or 60/40 or 30/70 or 70/30 or 20/80 or 80/20.
  • the DFS is used as an electrolyte in a fuel cell or as a portion of a fuel cell casing, or both.
  • a method comprising providing a DFS in a fuel cell system, wherein the DFS comprises 3YSZ (3 mol% Y 2 O 3 in ZrCh) and 8YSZ (8 mol% Y 2 O 3 in ZrCh), wherein the mass ratio of 3YSZ/8YSZ is in the range of from 100/0 to 0/100 or from 10/90 to 90/10 and wherein the DFS is impermeable to non-ionic substances and electrically insulating.
  • the mass ratio of 3YSZ/8YSZ is about 50/50 or 40/60 or 60/40 or 30/70 or 70/30 or 20/80 or 80/20.
  • the DFS is used as electrolyte or a portion of a fuel cell casing or both in the fuel cell system.
  • the portion of a fuel cell casing may be the entire fuel cell casing.
  • the portion of a fuel cell casing is a coating on the fuel cell casing. The electrolyte and said portion of a fuel cell casing are in contact.
  • a fuel cell system comprising an anode having six surfaces, a cathode having six surfaces, an electrolyte, and an anode surround in contact with at least three surfaces of the anode, wherein the electrolyte is part of the anode surround and said anode surround is made of the same material as the electrolyte.
  • said same material is a DFS comprising 3YSZ (3 mol% Y2O3 in ZrCh) and 8YSZ (8 mol% Y203 in ZrCh), wherein the mass ratio of 3YSZ/8YSZ is in the range of from 100/0 to 0/100 or from 10/90 to 90/10 and wherein the DFS is impermeable to non-ionic substances and electrically insulating.
  • the mass ratio of 3YSZ/8YSZ is about 50/50 or 40/60 or 60/40 or 30/70 or 70/30 or 20/80 or 80/20.
  • the anode surround is in contact with five surfaces of the anode.
  • the fuel cell system comprises a barrier layer between the cathode and a cathode surround, wherein the barrier layer is in contact with at least three surfaces of the cathode, wherein the electrolyte is part of the cathode surround and said cathode surround is made of the same material as the electrolyte.
  • the fuel cell system comprises fuel passage and oxidant passage in the anode surround and the cathode surround.
  • the fuel cell system comprises an interconnect, wherein the interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid dispersing components.
  • the fuel cell system comprises an interconnect, wherein the interconnect comprises no fluid dispersing element and said anode and cathode comprise fluid channels.
  • Fig. 10A illustrates an electrochemical (EC) gas producer.
  • EC gas producer device 1000 comprises first electrode 1010, electrolyte 1030 a second electrode 1020.
  • First electrode 1010 is configured to receive a fuel and no oxygen 1040.
  • Second electrode 1020 is configured to receive water or nothing as denoted by arrow 1050.
  • Device 1000 is configured to
  • first electrode 1010 and second electrode 1020 may comprise Ni-YSZ or NiO-YSZ.
  • Arrow 1040 represents an influx of hydrocarbon and water or hydrocarbon and carbon dioxide.
  • Arrow 1050 represents an influx of water or water and hydrogen.
  • electrode 1010 comprises Cu-CGO further optionally comprising CuO or CU2O or combinations thereof.
  • Electrode 1020 comprises Ni-YSZ or NiO-YSZ.
  • Arrow 1040 represents an influx of hydrocarbon with little to no water, with no carbon dioxide, and with no oxygen
  • 1050 represents an influx of water or water and hydrogen.
  • Fig. 10B illustrates an EC gas producer.
  • EC gas producer device 1001 comprises first electrode 1011, second electrode 1021, and electrolyte 1031 between the electrodes.
  • the first electrode 1011 is configured to receive a fuel and no oxygen 1040, wherein second electrode 021 is configured to receive water or nothing.
  • 1031 represents a proton conducting membrane
  • 1011 and 1021 represent Ni-barium zirconate electrodes.
  • no oxygen means there is no oxygen present at first electrode 1010, 1011 or at least not enough oxygen that would interfere with the reaction.
  • water only means that the intended feedstock is water and does not exclude trace elements or inherent components in water.
  • water containing salts or ions is considered to be within the scope of water only. Water only also does not require 100% pure water but includes this embodiment.
  • the hydrogen produced from second electrode 1020, 1021 is pure hydrogen, which means that in the produced gas phase from the second electrode, hydrogen is the main component.
  • the hydrogen content is no less than 99.5%.
  • the hydrogen content is no less than 99.9%.
  • the hydrogen produced from the second electrode is the same purity as that produced from electrolysis of water.
  • first electrode 1010, 1011 is configured to receive methane and water or methane and carbon dioxide.
  • said fuel comprises a hydrocarbon having a carbon number in the range of 1-12, 1-10 or 1-8. Most preferably, the fuel is methane or natural gas, which is predominantly methane.
  • the device does not generate electricity.
  • the device comprises a mixer configured to receive at least a portion of the first electrode product and at least a portion of the second electrode product. In an embodiment, said mixer is configured to generate a gas stream in which the hydrogen to carbon oxides ratio is no less than 2, or no less than 3 or between 2 and 3.
  • first electrode 1010, 1011 or second electrode 1020, 1021, or both comprise a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is no less than 1/100, or no less than 1/10, or no less than 1/5, or no less than 1/3, or no less than 1/1.
  • the catalyst comprises nickel oxide, silver, cobalt, cesium, nickel, iron, manganese, nitrogen, tetra-nitrogen, molybdenum, copper, chromium, rhodium, ruthenium, palladium, osmium, iridium, platinum, or combinations thereof.
  • the substrate comprises gadolinium, CeC> 2 , ZrC> 2 , SiC>2, T1O2, steel, cordierite (2MgO-2Al 2 C> 3 - 5S1O2), aluminum titanate (AI2T1O5), silicon carbide (SiC), all phases of aluminum oxide, yttria or scandia-stabilized zirconia (YSZ), gadolinia or samaria-doped ceria, or combinations thereof.
  • first electrode 1010, 1011 or second electrode 1020, 1021, or both comprise a promoter wherein the promoter comprises Mo, W, Ba, K, Mg, Fe, or combinations thereof.
  • the electrodes and electrolyte form a repeat unit.
  • a device may comprise two or more repeat units separated by interconnects.
  • the interconnects comprise no fluid dispersing element.
  • first electrode 1010, 1011 or second electrodel020, 1021, or both comprise fluid channels.
  • the first electrode or second electrode, or both comprise fluid dispersing components.
  • a assembly method comprising forming a first electrode, forming a second electrode, and forming an electrolyte between the electrodes, wherein the electrodes and electrolyte are assembled as they are formed. Forming comprises material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing, vat
  • the electrodes and electrolyte may form a repeat unit.
  • the method may further comprise forming two or more repeat units and forming interconnects between the two or more repeat units the assembly method may further comprise forming fluid channels or fluid dispersing components in the first electrode or the second electrode, or both.
  • the forming method comprises heating in situ.
  • the heating comprise EMR.
  • EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser or electron beam.
  • the first electrode is configured to receive a fuel and no oxygen, wherein the second electrode is configured to receive water only or nothing, wherein the device is configured to simultaneously produce hydrogen from the second electrode and syngas from the first electrode.
  • a method comprising providing a device comprising a first electrode, a second electrode, and an electrolyte between the electrodes, introducing a fuel without oxygen to the first electrode, introducing water only or nothing to the second electrode to generate hydrogen, extracting hydrogen from the second electrode, and extracting syngas from the first electrode.
  • the fuel comprises methane and water or methane and carbon dioxide.
  • the fuel comprises a hydrocarbon having a carbon number in the range of 1-12 or 1-10 or 1-8.
  • the method comprises feeding at least a portion of the extracted syngas to a Fischer-Tropsch reactor. In an embodiment, the method comprises feeding at least a portion of the extracted hydrogen to the Fischer-Tropsch reactor. In an embodiment, the at least portion of the extracted syngas and the at least portion of the extracted hydrogen are adjusted such that the hydrogen to carbon oxides ratio is no less than 2, or no less than 3, or between 2 and 3. [242] In an embodiment, the fuel is directly introduced into the first electrode or water is directly introduced into the second electrode, or both.
  • the first electrode or second electrode, or both comprise a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is in no less than 1/100, or no less than 1/10, or no less than 1/5, or no less than 1/3, or no less than 1/1.
  • the catalyst comprises nickel oxide, silver, cobalt, cesium, nickel, iron, manganese, nitrogen, tetra-nitrogen, molybdenum, copper, chromium, rhodium, ruthenium, palladium, osmium, iridium, platinum, or combinations thereof.
  • the substrate comprises gadolinium,
  • the method comprises applying a potential difference between the electrodes.
  • the method comprises using the extracted hydrogen in one of the following reactions, or combinations thereof: Fischer-Tropsch (FT) reaction, dry reforming reactions, Sabatier reaction catalyzed by nickel, Bosch reaction, reverse water gas shift reaction, electrochemical reaction to produce electricity, production of ammonia and/or fertilizer, electrochemical compressor for hydrogen storage or fueling hydrogen vehicles, or hydrogenation reactions.
  • FT Fischer-Tropsch
  • dry reforming reactions dry reforming reactions
  • Sabatier reaction catalyzed by nickel Bosch reaction
  • reverse water gas shift reaction reverse water gas shift reaction
  • electrochemical reaction to produce electricity production of ammonia and/or fertilizer
  • electrochemical compressor for hydrogen storage or fueling hydrogen vehicles or hydrogenation reactions.
  • the gas producer is not a fuel cell and does not generate electricity, in various embodiments. Electricity may be applied to the gas producer at the anode and cathode in some cases. In other cases, electricity is not needed.
  • Both the cathode and the anode are electrodes in the EC gas producer. Examples of anode and cathode materials are discussed below. In an operating device, the actual anode and cathode designation depends on where reduction and oxidation reactions take place. In certain embodiments, a material acts as an anode with a set of operating conditions and/or feedstocks and the same material also acts as a cathode but with a different set of operating conditions and/or feedstocks. As such, the listing of materials for anode or cathode is not limiting. Furthermore, the listings of anode/cathode materials apply to the first electrode and second electrode as discussed above.
  • the cathode comprises perovskites, such as LSC, LSCF, LSM. In some embodiments, the cathode comprises lanthanum, cobalt, strontium or manganite or combinations thereof. In an embodiment, the cathode is porous. In an embodiment, the cathode comprises one or more of YSZ, nitrogen, nitrogen boron doped Graphene,
  • the cathode comprises LSCo, LCo, LSF, LSCoF.
  • the cathode comprises perovskites LaCo03, LaFe03, LaMn03, (La,Sr)Mn03, LSM-GDC, LSCF-GDC, LSC-GDC.
  • Cathodes containing LSCF are suitable for intermediate-temperature electrochemical gas producer operation.
  • the cathode comprises Cu-CGO, CuO-CGO, CU2O-CGO, or
  • the cathode comprises a material selected from the group consisting of lanthanum strontium manganite, lanthanum strontium ferrite, and lanthanum strontium cobalt ferrite. In a preferred embodiment, the cathode comprises lanthanum strontium manganite.
  • the cathode comprises Ba(Ceo. 4 Pro. 4 Yo. 2 )C> 3 ; PrBaCuFeOs;
  • the cathode is a composite comprising Bao. 5 Sro. 5 Coo. 5 Feo. 5 O 3 and BZCY (for example in a weight ratio of 3:2), wherein BZCY is
  • the cathode is a composite comprising
  • the cathode is a composite comprising Smo.sSro.sCoOs and BZCY (for example in a weight ratio of 7:3).
  • the anode comprises nickle-oxide, nickle-oxide-YSZ, NiO-GDC, NiO-SDC, aluminum doped zinc oxide, molybdenum oxide, lanthanum, strontium, chromite, ceria, perovskites (such as, LSCF [La ⁇ l-x ⁇ Sr ⁇ x ⁇ Co ⁇ l-y ⁇ Fe ⁇ y ⁇ 03] or LSM [La ⁇ l-x ⁇ Sr ⁇ x ⁇ Mn03], where x is usually 0.15-0.2 and y is 0.7 to 0.8).
  • the anode comprises SDC or BZCYYb coating or barrier layer to reduce coking and sulfur poisoning.
  • the anode is porous.
  • the anode comprises a combination of electrolyte and electrochemically active material, or a combination of electrolyte and electrically conductive material.
  • the anode comprises nickel and yttria stabilized zirconia. In a preferred embodiment, the anode is formed by reduction of a material comprising nickel oxide and yttria stabilized zirconia. In a preferred embodiment, the anode comprises nickel and gadolinium stabilized ceria. In another preferred embodiment, the anode is formed by reduction of a material comprising nickel oxide and gadolinium stabilized ceria.
  • the anode comprises NiO or NiO-BZCY (1:1) and a pore former, NiO-BZCY (6:4) and corn starch, NiO-BZCY (6:4) and starch/NiO-BZCY (6:4), NiO-BZCY (6:4) NiO- BZCY or NiO-BZCY (6:4) and starch/NiO-BZCY (1:1).
  • the anode comprises Cu-CGO, CuO-CGO, CU2O-CGO, or combinations thereof.
  • an EC compressor comprising an anode, a cathode, an electrolyte between the anode and the cathode, a porous bipolar plate (PBP), an integrated support, a fluid distributor at a first end of the compressor, and a fluid collector at a second end of the compressor, wherein the support is impermeable to non-ionic substances and electrically insulating.
  • the PBP is electrically conductive and permeable to gases (such as H2, O2).
  • Fig. IOC illustrates an electrochemical compressor.
  • EC compressor 1080 comprises anode 1081, cathode 1082, electrolyte 1083, and PBP 1084 to form a repeat unit.
  • an electrochemical compressor comprises a two or more repeat units to form a multiplicity of repeat units between the fluid distributor 1085 and the fluid collector 1086.
  • the EC compressor is configured to provide between the first end and the second end of the compressor a fluid pressure differential no less than 4000 psi, or no less than 5000 psi, or no less than 6000 psi, or no less than 7000 psi, or no less than 8000 psi, or no less than 9000 psi, or no less than lOOOOpsi.
  • said support is part of the electrolyte, or the anode, or the cathode, or the PBP, or combinations thereof.
  • the support has a lattice structure that is regular or irregular.
  • the anode or cathode, or both the anode and cathode comprise fluid channels.
  • the anode, or cathode, or both the anode and cathode comprise fluid dispersing components.
  • an EC compressor comprising depositing an anode, a cathode, an electrolyte between the anode and the cathode, and a porous bipolar plate (PBP) to form the EC compressor.
  • the method comprises providing a fluid distributor at a first end of the compressor and a fluid collector at a second end of the compressor.
  • Thedeposition comprises material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing, vat photopolymerization, powder bed fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing, or combinations thereof.
  • the deposition method comprises co-sintering the anode, the cathode, the electrolyte, and the PBP.
  • the deposition method comprises heating in situ.
  • the heating comprises EMR.
  • the EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser, electron beam.
  • the method may further comprise depositing an integrated support, wherein the support is impermeable to non-ionic substances and electrically insulating.
  • the support may have a lattice structure that is regular or irregular.
  • said support is part of the electrolyte, or the anode, or the cathode, or the PBP, or combinations thereof.
  • the method comprises forming fluid dispersing components or fluid channels in the anode, or cathode, or both the anode and cathode.
  • an EC compressor that comprises an anode, a cathode, an electrolyte between the anode and the cathode, a porous bipolar plate (PBP), an integrated support, a fluid distributor at a first end of the compressor, and a fluid collector at a second end of the compressor, wherein the support is impermeable to non-ionic substances and electrically insulating.
  • PBP porous bipolar plate
  • the EC compressor provides between the first end and the second end of the compressor a fluid pressure differential no less than 4000 psi, or no less than 5000 psi, or no less than 6000 psi, or no less than 7000 psi, or no less than 8000 psi, or no less than 9000 psi, or no less than lOOOOpsi.
  • the EC compressor increases the pressure of hydrogen or oxygen from the first end to the second end.
  • the method of using the EC compressor comprises using the compressor for hydrogen storage. In a preferred embodiment, the method comprises using the compressor for fueling vehicles. In a preferred embodiment, the method comprises using the compressor in pressurized hydrogen refrigeration systems.
  • All layers of an EC compressor which is illustrated in Fig. IOC, may be formed and assembled via printing.
  • the material for making the anode, the cathode, the electrolyte, the PBP, and the integrated support, respectively, is made into an ink form comprising a solvent and particles (e.g., nanoparticles).
  • the ink optionally comprises a dispersant, a binder, a plasticizer, a surfactant, a co-solvent, or combinations thereof.
  • NiO and YSZ particles are mixed with a solvent, wherein the solvent is water (e.g., de-ionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used.
  • YSZ particles were mixed with a solvent, wherein the solvent is water (e.g., de-ionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used to form the electrolyte and support.
  • the solvent may include water (e.g., de-ionized water), organic solvents (e.g. mono-, di-, or tri-ethylene glycols or higher ethylene glycols, propylene glycol, 1,4- butanediol or ethers of such glycols, thiodiglycol, glycerol and ethers and esters thereof, polyglycerol, mono-, di-, and tri-ethanolamine, propanolamine, N,N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, 1,3-dimethylimidazolidone, methanol, ethanol, isopropanol, n-propanol, diacetone alcohol, acetone, methyl ethyl ketone, propylene carbonate), and combinations thereof.
  • water e.g., de-ionized water
  • organic solvents e.g. mono-, di-, or tri-ethylene glycols or
  • the method and system of this disclosure are suitable for making a catalyst or a catalyst composite, such as a Fischer-Tropsch (FT) catalyst or catalyst composite.
  • a Fischer-Tropsch (FT) catalyst composite comprising a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is in no less than 1/100, or no less than 1/10, or no less than 1/5, or no less than 1/3, or no less than 1/1.
  • the catalyst comprises Fe, Co, Ni, or Ru.
  • the substrate comprises AI2O3, ZrC>2, S1O2, T1O2, CeC>2, modified AI2O3, modified ZrC>2, modified S1O2, modified T1O2, modified CeC>2, gadolinium, steel, cordierite (2Mg0-2Al203-5SiC>2), aluminum titanate (AI2T1O5), silicon carbide (SiC), all phases of aluminum oxide, yttria or scandia-stabilized zirconia (YSZ), gadolinia or samaria-doped ceria, or combinations thereof.
  • the catalyst composite comprises a promoter wherein the promoter comprises noble metals, metal cations, or combinations thereof.
  • the promoter may comprise B, La, Zr, K, Cu, or combinations thereof.
  • the catalyst composite comprises fluid channels or alternatively fluid dispersing components.
  • the FT reactor/system is miniaturized compared to traditional FT reactors/systems.
  • a method comprising depositing a FT catalyst to a substrate to form a FT catalyst composite, wherein said depositing comprises material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing, vat photopolymerization, powder bed fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing, or combinations thereof.
  • the mass ratio between the catalyst and the substrate is in no less than 1/100, or no less than 1/10, or no less than 1/5, or no less than 1/3, or no less than 1/1.
  • the deposition method comprises forming fluid channels or alternatively fluid dispersing components in the catalyst composite.
  • a system comprising a Fischer-Tropsch (FT) reactor containing a FT catalyst composite comprising a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is in no less than 1/100, or no less than 1/10, or no less than 1/5, or no less than 1/3, or no less than 1/1.
  • the catalyst comprises Fe, Co, Ni, or Ru.
  • the substrate comprises AI2O3, ZrC>2, S1O2, T1O2, CeC>2, modified AI2O3, modified ZrC>2, modified S1O2, modified T1O2, modified CeC>2, gadolinium, steel, cordierite (2Mg0-2Al203-5SiC>2), aluminum titanate (AI2T1O5), silicon carbide (SiC), all phases of aluminum oxide, yttria or scandia-stabilized zirconia (YSZ), gadolinia or samaria- doped ceria, or combinations thereof.
  • the catalyst composite comprises a promoter.
  • a FT catalyst composite is formed via printing.
  • the catalyst and the substrate/support are made into an ink form comprising a solvent and particles (e.g., nanoparticles).
  • the ink optionally comprises a dispersant, a binder, a plasticizer, a surfactant, a co-solvent, or combinations thereof.
  • the ink may be any kind of suspension.
  • the ink may be treated with a mixing process, such as ultrasonication or high shear mixing.
  • an iron ink is in an aqueous environment.
  • an iron ink is in an organic solvent
  • the iron ink may also include a promoter.
  • the substrate/support may be a suspension or ink of alumina, in an aqueous environment or an organic environment.
  • the substrate ink may be treated with a mixing process, such as ultrasonication or high shear mixing.
  • the substrate ink comprises a promoter.
  • the promoter is added as its own ink, in an aqueous environment or an organic environment.
  • the various inks are printed separately and sequentially. In some cases, the various inks are printed separately and simultaneously, for example, through different print heads. In some cases, the various inks are printed in combination as a mixture.
  • an exhaust from the fuel cell comprises hydrogen, carbon dioxide, water, and optionally carbon monoxide.
  • the exhaust is passed over a FT catalyst (e.g., an iron catalyst) to produce synthetic fuels or lubricants.
  • a FT catalyst e.g., an iron catalyst
  • the FT iron catalyst has the property to promote water gas shift reaction or reverse water gas shift reaction.
  • the FT reactions take place at a temperature in the range of 150-350 °C and a pressure in the range of one to several tens of atmospheres (e.g., 15 atm or 10 atm or 5 atm or 1 atm). Additional hydrogen may be added to the exhaust stream to reach a hydrogen to carbon oxides ratio (carbon dioxide and carbon monoxide) of no less than 2 or no less than 3 or between 2 and 3.
  • Fig. 13A illustrates an impermeable interconnect 1302 with a fluid dispersing component 1304.
  • Fig. 13B illustrates an impermeable interconnect 1302 with two fluid dispersing components 1304.
  • the fluid dispersing components 1304 are in contact with both sides (major faces) of interconnect 1302. As such, the interconnect is shared between two repeat units in an electrochemical reactor. Fluid dispersing components 1304 function to distribute fluids, e.g., reactive gases (such as methane, hydrogen, carbon monoxide, air, oxygen, etc.), in an electrochemical reactor. As such, traditional interconnects with channels are no longer needed. The design and manufacturing of such traditional interconnects with channels is complex and expensive.
  • the interconnects are simply impermeable layers that conduct or collect electrons.
  • Figs. 13C-F schematically illustrate segmented fluid dispersing components 1304 on top of impermeable interconnect 1302. Such segments may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The segments may be discontinuous.
  • Fig. 13C illustrates segmented fluid dispersing components 1304 of similar shapes but different sizes on an impermeable interconnect 1302.
  • Fig. 13D illustrates segmented fluid dispersing components 1304 of similar shapes and similar sizes on an impermeable interconnect 1302.
  • FIG. 13E illustrates segmented fluid dispersing components 1304 of similar shapes and similar sizes but closely packed on an impermeable interconnect 1302.
  • Fig. 13F illustrates segmented fluid dispersing components 1304 of different shapes and different sizes on an impermeable interconnect 1302. It is also contemplated that these segments have different compositions, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof.
  • Figs. 13G-I schematically illustrates an impermeable interconnect 1302 with fluid dispersing component 1304. Further illustrated are different fluid inlet and out designs.
  • the fluid dispersing components may have varying density, porosity, pore size, pore shape, composition, or permeability, or combinations thereof, in different portions (e.g., in the lateral direction or perpendicular to the lateral direction). Such variabilities provide control and adjustability of the fluid flow in the fluid dispersing component.
  • Fig. 13G illustrates an impermeable interconnect 1302 and fluid dispersing component 1304.
  • Fig. 13H illustrates an impermeable interconnect 1302 and fluid dispersing component 1304.
  • Fig. 13G-I illustrates an impermeable interconnect 1302 and fluid dispersing component 1304.
  • 1306 and 1308 in Figs. 13G-I represent different inlet and outlet designs.
  • the interconnect 1302 has matching inlet and outlet for each configuration.
  • 1306 represents a fluid inlet
  • 1308 represents a fluid outlet.
  • the fluid flow is denoted by arrows 1310.
  • Fig. 13J illustrates an impermeable interconnect 1302 and a fluid dispersing component 1304. Further illustrated in Fig. 13J are alternative fluid flow designs as shown by the arrows. For example, the fluid may flow from left to right across the fluid dispersing component; or the fluid may flow from front to back across the fluid dispersing component.
  • Fig. 13K illustrates a fluid dispersing component 1304.
  • Fluid dispersing component 1304 design comprises four corners labeled A, B, C, and D.
  • Location A comprises Fluid flow inlet 1312.
  • Location B comprises fluid flow outlet 1314.
  • an electrochemical reactor e.g., a fuel cell
  • an electrochemical reactor e.g., a fuel cell
  • the fuel cell comprises two FDC's.
  • the two FDC's may be symmetrically placed in contact with the interconnect on its opposing side or opposing major faces.
  • the interconnect is shared between the two repeat units in the electrochemical reactor, each repeat unit comprising one of the two FDC's.
  • the FDC may be a foam, open cell foam, or comprises a lattice structure.
  • the FDC is segmented wherein the segments have different compositions, materials, shapes, sizes, densities, porosities, pore sizes, pore shapes,
  • the shapes of the segments may comprise pillar, hollow cylinder, cube, rectangular cuboid, trigonal trapezohedron, quadrilateral frustum, parallelepiped, triangular bipyramid, tetragonal anti-wedge, pyramid, pentagonal pyramid, prism, or combinations thereof.
  • the FDC has varying density, porosity, pore size, pore shape, permeability, or combinations thereof wherein the density, porosity, pore size, pore shape, or permeability or combination thereof is controlled.
  • the density, porosity, pore size, pore shape, or permeability or combination thereof is controlled to adjust flow of a fluid through the FDC. In other embodiments, the density, porosity, pore size, pore shape, or permeability or combination thereof is controlled to cause uniform fluid flow from a first point in the FDC to a second point in the FDC.
  • the fluid flow pattern may be adjusted as desired. For example, it does not need to be uniform.
  • the fluid flow may be increased or decreased according to the reactivities of the FDC or reaction rates of the fluid in the various portions of the FDC.
  • the fluid flow may be increased or decreased according to the fluid flow rates to an anode or a cathode in the various portions of the FDC.
  • the fluid flow may be increased or decreased according to the reaction rates in an anode or a cathode related to or in contact with the various portions of the FDC.
  • density is higher in the center of the FDC. In an embodiment, density is lower in the center of the FDC. In an embodiment, porosity or permeability or pore throat size is lower toward the center of the FDC. In an embodiment, porosity or permeability or pore throat size is higher toward the center of the FDC.
  • the FDC is part of an anode or part of a cathode.
  • the FDC is an anode or a cathode.
  • the impermeable interconnect has a thickness of no greater than 10 microns, or no greater than 1 micron, or no greater than 500 nm.
  • the impermeable interconnect comprises inlets and outlets for fluids.
  • the fluids comprise reactants for the fuel cell.
  • a method of making a fuel cell comprising (a) forming an impermeable interconnect having no fluid dispersing element; (b) forming an electrolyte; (c) forming a fluid dispersing component (FDC); and (d) placing the FDC between the interconnect and the electrolyte.
  • the FDC is formed by creating a multiplicity of segments and assembling the segments.
  • the segments have different compositions, materials, shapes, sizes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof wherein the shapes comprise a pillar, hollow cylinder, cube, rectangular cuboid, trigonal trapezohedron, quadrilateral frustum, parallelepiped, triangular bipyramid, tetragonal anti-wedge, pyramid, pentagonal pyramid, prism, or combinations thereof.
  • the FDC may be a foam, open cell foam; or comprises a lattice structure.
  • the method of forming the FDC comprises varying density, porosity, pore size, pore shape, permeability, or combinations thereof.
  • the method comprises controlling the density, porosity, pore size, pore shape, permeability, or combinations thereof of the FDC.
  • the method may comprise controlling density, porosity, pore size, pore shape, permeability, or combinations thereof of the FDC to adjust flow of a fluid through the FDC.
  • the method may comprise controlling density, porosity, pore size, pore shape, permeability, or combinations thereof of the FDC to cause uniform fluid flow from a first point in the FDC to a second point in the FDC.
  • the method may comprise controlling density, porosity, pore size, pore shape, permeability, or combinations thereof of the FDC to cause patterned fluid flow from a first point in the FDC to a second point in the FDC.
  • the fluid flow pattern may be adjusted as desired. For example, it does not need to be uniform.
  • the fluid flow may be increased or decreased according to the reactivities of the FDC or reaction rates of the fluid in the various portions of the FDC.
  • the fluid flow may be increased or decreased according to the fluid flow rates to an anode or a cathode in the various portions of the FDC.
  • the fluid flow may be increased or decreased according to the reaction rates in an anode or a cathode related to or in contact with the various portions of the FDC.
  • step (c) comprises varying composition of material used to form the FDC. In an embodiment, step (c) comprises varying particles size used to form the FDC. In an embodiment, step (c) comprises heating different portions of the FDC to different
  • said heating comprises electromagnetic radiation (EMR).
  • EMR electromagnetic radiation
  • EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser or electron beam.
  • steps (a)-(d) or steps (b)-(d) are performed using additive
  • AM comprises extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition or lamination or combinations thereof.
  • the method of forming the FDCs comprises heating the fuel cell such that shrinkage rates of the FDC and the electrolyte are matched or such that shrinkage rates of the interconnect, the FDC, and the electrolyte are matched.
  • the heating comprises EMR.
  • EMR comprises UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser or electron beam or combinations thereof.
  • heating is performed in situ. In preferred embodiments, heating takes place for no greater than 30 minutes, or no greater than 30 seconds, or no greater than 30 milliseconds.
  • the FDC is part of an anode or part of a cathode.
  • the FDC is an anode or a cathode.
  • the impermeable interconnect has a thickness of no greater than 10 microns, or no greater than 1 micron, or no greater than 500 nm.
  • the impermeable interconnect has a thickness of no greater than 10 microns, or no greater than 1 micron, or no greater than 500 nm.
  • interconnect comprises inlets and outlets for fluids. More preferably, the fluids comprise reactants for the fuel cell.
  • a method comprising providing a template wherein the template is in contact with an electrode material; and removing at least a portion of the template to form channels in the electrode material.
  • Fig. 14A illustrates a template 1400 for making channeled electrodes. Such templates may be removed by oxidation, melting, vaporization, reduction, or any suitable means, either after the electrochemical reactor is made or at the start of the utilization of the reactor.
  • the channeled electrode material comprises NiO, YSZ, GDC, LSM, LSCF, or combinations thereof.
  • providing a template comprises printing the template or precursors that assemble to form the template.
  • Providing a template comprises polymerizing one or more monomers or a photo-initiator, or both.
  • the method comprises curing monomers and/or oligomers, through internal or external techniques.
  • internal techniques include polymerization by free radical molecular initiation, and/or initiation by in situ reduction/oxidation.
  • external techniques include photolysis, exposure to ionizing radiation, (ultra)sonication and thermal decomposition to form the initiator species.
  • said curing comprises UV curing.
  • the method comprises adding a polymerizing agent, wherein the polymerizing agent comprises a photo-initiator.
  • the polymerizing agent is printed on top of the monomer or printed within each slice of the monomer.
  • providing a template comprises dispersing metal oxide particles in a monomer ink before printing the template.
  • the metal oxide comprises NiO, CuO, LSM (lanthanum strontium manganite), LSCF (lanthanum strontium cobalt ferrite), GDC (gadolinium doped ceria), SDC (samaria-doped ceria), or combinations thereof.
  • said monomer comprises alcohol, aldehyde, carboxylic acid, ester, and/or ether functional groups.
  • said template comprises NiO, Cu(l)0, Cu(ll)0, an organic compound, a photopolymer, or combinations thereof.
  • removing at least a portion of the template comprises heating, combustion, solvent treatment, oxidation, reduction, or combinations thereof.
  • the combustion leaves no deposits and is not explosive.
  • the reduction takes place in a metal oxide and produces porous template.
  • the method of providing a template comprises heating in situ.
  • the template and electrode material are printed slice by slice and a second slice is printed atop a first slice before the first slice is heated, wherein the heating removes at least a portion of the template.
  • the heating comprises EMR.
  • EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser, electron beam.
  • the channels and the electrode material form an electrode layer.
  • the channels have regular trajectories within the electrode layer. For example, the channels are parallel to one another. The channels may run from one end, edge, orcorner of the electrode layer to the opposite end, edge or corner.
  • the channels may run from one end, edge or corner of the electrode, turn 90 degrees to another end, edge or corner.
  • the channels have random trajectories within the electrode layer. For example, the channels may have tortuous trajectories with no regularities.
  • the channels may have more than one entry point and more than one exit point. The more than one entry point and the more than one exit point are distributed across the electrode layer.
  • the entry points and the exits points of the channels in the electrode layer may be on any side of the electrode layer, including the top surface or side and the bottom surface or side.
  • the volume fraction of the template in the electrode layer is in the range of 5%-95%, or 10%-90%, or 20%-80%, or 30%-70%, or 40%-60%.
  • the volume fraction of the channels in the electrode layer is in the range of 10%-90%, or 20%-80%, or 30%-70%, or 40%-60%.
  • the total effective porosity of the electrode layer with channels is preferably in the range of 20%-80%, or 30%-70%, or 40%-60%. Such total effective porosity of the electrode layer with channels is no less than the porosity of the electrode material.
  • the tortuosity of the electrode layer with channels is no greater than the native tortuosity of the electrode material.
  • the gas channels span the height of the electrode layer.
  • the gas channels may occupy a height that is less than that of the electrode layer.
  • the electrode layer is about 50 microns thick.
  • the gas channel width is no less than 10 microns. In an embodiment, the gas channel width is no less than 100 microns.
  • a method comprising (a) printing a first template and a first electrode material to form a first electrode layer, wherein the first template is in contact with the first electrode material; (b) printing an electrolyte layer; (c) printing a second template and a second electrode material to form a second electrode layer, wherein the second template is in contact with the second electrode material; and (d) printing an interconnect.
  • the steps are performed in any sequence.
  • the method comprises repeating steps (a)-(d) in any sequence to form a stack or a repeat unit of a stack.
  • the method comprises (e) removing at least a portion of the first template and of the second template to form channels in the first and second electrode layers.
  • the removing comprises heating, combustion, solvent treatment, oxidation, reduction, or combinations thereof.
  • the removing takes place in situ.
  • Removing may take place after a stack or a repeat unit of a stack is printed. Removing may take place when a stack is initiated to operate.
  • the printing takes place slice by slice and a second slice is printed atop a first slice before the first slice is heated, wherein the heating removes at least a portion of the template.
  • the printing step comprises material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing, or combinations thereof.
  • a method comprising (a) printing a first electrode layer; (b) printing an electrolyte layer; (c) printing a second electrode layer; and (d) printing an interconnect.
  • the printing comprises material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing.
  • the steps are performed in any sequence.
  • the method comprises repeating steps (a)-(d) in any sequence to form a stack or a repeat unit of a stack.
  • a method comprising aerosol jetting or aerosol jet printing an electrode layer, or an electrolyte layer, or an interconnect, or combinations thereof.
  • Fig. 14B is a cross-sectional view of a half cell between a first interconnect and an electrolyte.
  • the stack in Fig. 14B comprises a bottom/first interconnect 1401, an optional layer that contains the bottom interconnect material and first electrode material 1402, first electrode segments 1403, first filler materials that form a first template 1404 and electrolyte 1405.
  • Fig. 14C is a cross-sectional view of a half cell between a second interconnect and an electrolyte, comprising electrolyte 1405, second electrode segments 1406, filler materials that forms a second template 1407 and a top/second interconnect 1408.
  • the views shown in Fig. 14B and Fig. 14C are perpendicular to one another.
  • Fig. 14D is a cross-sectional view of a half cell between a first interconnect and an electrolyte, comprising bottom interconnect 1401, an optional layer that contains the bottom interconnect material and first electrode material 1402, first electrode segments 1403, first filler materials that forms a first template 1404, electrolyte 1405 and optional shields 1409 for the first filler materials when the first electrode is heated and/or sintered.
  • Fig. 14E is a cross-sectional view of a half cell between a second interconnect and an electrolyte, comprising electrolyte 1405, second electrode segments 1406, filler materials that forms a second template 1407, top interconnect 1408 and optional shields for the second filler materials when the top interconnect is heated and/or sintered.
  • the views shown in Fig. 14D and Fig. 14E are perpendicular to one another.
  • 1405 represents an electrolyte with a barrier for the first electrode or for second electrode.
  • 1409 represents optional shields for the first fillers when the first electrode is heated/sintered.
  • 1410 represents optional shields for the second fillers when the top interconnect is
  • electrolyte 1405 or electrolyte-barrier layer is in contact with the first electrode and the second electrode continuously along its opposing major faces.
  • the shapes of the electrode segments and the fillers in these cross-sectional views are only representative and not exact. They may take on any regular or irregular shapes.
  • the fillers and/or templates are removed when the electrochemical reactor is made (e.g., a fuel cell stack or a gas producer), for example, via heating in a furnace. Or alternatively, they are removed when the electrochemical reactor is initiated into operation via hot gas/fluid passing through, using the effects of oxidation, melting, vaporization, gasification, reduction, or combinations thereof. These removed fillers and/or templates become channels in the electrodes.
  • multiple tiers of channels are present in an electrode.
  • an electrode is 25 microns thick with a multiplicity of channels having a height of 20 microns.
  • an electrode is 50 microns thick with a multiplicity of channels in 2 tiers, each tier of channels having a height of 20 microns.
  • the fillers comprise carbon, graphite, graphene, cellulose, metal oxides, polymethyl methacrylate, nano diamonds, or combinations thereof.
  • a unit in an electrochemical reactor comprising an interconnect, a first electrode, an electrolyte, and a second electrode is made via this method: providing the interconnect, depositing a first electrode material in segments on the interconnect, sintering the first electrode material, depositing a first filler material between the first electrode material segments, depositing additional first electrode material to cover the filler material, sintering the additional first electrode material and forming the first electrode, depositing an electrolyte material on the first electrode, sintering the electrolyte material to form the electrolyte, depositing a second electrode material on the electrolyte such that a multiplicity of valleys are formed in the second electrode material, sintering the second electrode material to form the second electrode, depositing a second filler material in the valleys of the second electrode, depositing a second interconnect material to cover the second electrode and the second filler material, and sintering the second interconnect material.
  • deposition is performed using inkjet printing or ultrasonic inkjet printing.
  • sintering is performed using electromagnetic radiation (EMR).
  • EMR electromagnetic radiation
  • the first and second filler materials absorb little to no EMR; the absorption is so minimal that the filler materials have no measurable change.
  • shields are deposited to cover the first filler material or the second filler material or both so that the heating and/or sintering process for the layer on top does not cause measurable change in the first filler material or the second filler material or both.
  • the shields comprise YSZ, SDC, SSZ, CGO, NiO-YSZ, Cu, CuO, CU2O, LSM, LSCF, lanthanum chromite, stainless steel, LSGM, or combinations thereof.
  • Figs. 15A-D illustrates various embodiments of electrodes having dual porosities with one, two or three layers shown in detail.
  • Fig. 15A schematically illustrates segments of fluid dispersing components in a first layer.
  • First layer 1500 comprises fluid dispersing component segments 1502. Segments 1502 may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof.
  • Volume fraction of channels (VFc) relative to layer 1500 containing the channels is also shown.
  • an electrode in an EC reactor comprising a material and channels, wherein the material and channels form a first layer in the electrode having a first layer porosity. The material has a material porosity.
  • the channels have a volume fraction VFc, which is the ratio between the volume of the channels and the volume of the first layer.
  • the first layer porosity refers to the average porosity of the first layer as a whole.
  • the first layer porosity is at least 5% greater than the material porosity.
  • the VFc is in the range of 0-99%, or 1-30%, or 10-90%, or 5-50%, or 3-30%, or 1-50%.
  • the VFc is no less than 5%, or 10%, or 20%, or 30%, or 40%, or 50%.
  • Fig. 15B schematically illustrates fluid dispersing components in a first layer along with a second layer in an electrode.
  • Electrode embodiment in Fig. 15B shows a first layer 1504 of fluid dispersing component segments 1505 and a second layer 1506.
  • the segments, as shown in Fig. 15B, may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof.
  • the electrode comprises a second layer wherein the second layer has a second layer porosity.
  • the second layer porosity refers to the average porosity of the second layer as a whole. In an embodiment, said second layer porosity is no greater than the first layer porosity or the second layer porosity is no less than the first layer porosity.
  • the second layer 1506 may comprise the same material as in the first layer.
  • the second layer 1506 may also comprise variabilities in compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof in the lateral direction or perpendicular to the lateral direction.
  • Fig. 15D schematically illustrates fluid dispersing components in a first layer 1508 along with a second layer 1512.
  • the electrode embodiment in Fig. 15D is similar to the embodiment in Fig. 15B.
  • the electrode in Fig. 15D comprises a first layer 1508 further comprising fluid dispersing component segments 1510, wherein segments 1510 may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof.
  • the second layer 1512 may comprise the same material as in the first layer.
  • the second layer 1512 may also comprise variabilities in compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof in the lateral direction or perpendicular to the lateral direction.
  • Fig. 15C schematically illustrates fluid dispersing components in a first layer along with a second and third layer.
  • Electrode embodiment in Fig. 15C comprises a first layer 1514, second layer 1516 and a third layer 1518.
  • the second layer and the third layer are on two sides of the first layer.
  • the second layer and the third layer are in continuous contact with two sides of the first layer.
  • First layer 1514 may comprises segments 1520 that have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof.
  • the second layer or the third layer may comprise the same material as in the first layer.
  • the second layer or the third layer may also comprise variabilities in compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof in the lateral direction or perpendicular to the lateral direction.
  • the material porosity of the first, second or third layer is in the range of 20-60%, in the range of 30-50%, in the range of 30-40% or in the range of 25-35%. In an embodiment, the material porosity is no less than 25%, or 35%, or 45%.
  • the electrode has a thickness of no greater than 10 cm, or 5 cm, or 1 cm. In an embodiment, the electrode has a thickness of no greater than 8 mm, or 5 mm, or 1 mm. In an embodiment, the electrode has a thickness of no greater than 100 microns, or 80 microns, or 60 microns.
  • contribution to the permeability of the first layer from the channels is greater than contribution to the permeability of the first layer from the material. In an embodiment, no less than 50%, or 70%, or 90% of the permeability of the first layer is due to the permeability of the channels. In an embodiment, permeability of the material in the first layer is no greater than 50%, or no greater than 10%, or no greater than 1%, or no greater than 0.001% of the permeability of the channels in the first layer.
  • an electrically conductive component (ECC) of an electrochemical reactor comprising: (a) depositing on a substrate a first composition comprising a first pore former with a first pore former volume fraction VFpl; (b) depositing on the substrate a second composition comprising a second pore former with a second pore former volume fraction VFp2, wherein said first composition and second composition form a first layer in the ECC; and (c) heating the first layer such that the first pore former and the second pore former become empty spaces.
  • said VFpl is in the range of 0-100%, or 10-90%, or 30-70%, or 50-100%, or 90-100%.
  • the VFp2 is in the range of 0-100%, or 0-70%, or 25-75%, or 30-60%.
  • the heating comprises reduction reactions or oxidation reactions, or both reduction and oxidation reactions.
  • Fig. 16 is an illustrative example of an electrode having dual porosities.
  • Fig. 16 shows EC device 1600 comprising a channeled electrode having dual porosities.
  • Device 1600 comprises an anode gas inlet 1601, an anode gas outlet 1602, a cathode gas inlet 1603, and a cathode gas outlet 1604.
  • Exploded view 1605 is a view of a portion of a cathode layer.
  • View 1606 is a closer view of the cathode wherein view 1606 represents a slice through the cathode layer that is composed of cathode 1607.
  • Cathode 1607 is a porous cathode that is formed using micro pore formers.
  • Channels 1608 represents channels formed from macro pore formers.
  • (a) and (b) are accomplished via printing, or via extrusion, or via additive manufacturing (AM), or via tape casting, or via spraying, or via deposition, or via sputtering, or via screen printing.
  • said additive manufacturing comprises extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition, lamination.
  • the first pore former and the second pore former are the same. In an embodiment, the first pore former and the second pore former are different. In an embodiment, said first pore former or second pore former has an average diameter in the range of 10 nm to 1 mm or 100 nm to 100 microns or 500 nanometers to 50 microns. In an embodiment, said first pore former or second pore former has a size distribution. In an embodiment, said first pore former or second pore former comprises carbon, graphite, polymethyl methacrylate (PMMA), cellulose, metal oxides, or combinations thereof.
  • PMMA polymethyl methacrylate
  • the method comprises repeating (a) and (b) to form a second layer in the ECC; and heating the second layer.
  • heating the second layer takes places at the same time as heating the first layer.
  • heating the second layer takes places at a different time as heating the first layer.
  • heating the second layer and heating the first layer have at least a portion of overlapping time period.
  • the method comprises repeating (a) and (b) to form a third layer in the ECC; and heating the third layer.
  • the second layer and the third layer are on two sides of the first layer.
  • heating the first, second, and third layers is simultaneous.
  • the first, second, and third layers are heated at different times.
  • heating of the first, second, and third layers has overlapping time periods.
  • the first, second, or third layer is heated more than once.
  • the channels have a volume fraction VFc, which is the ratio between the volume of the channels and the volume of the first layer.
  • said VFc is in the range of 0-99% or 1-30% or 10-90% or 5-50% or 3-30% or 1-50%. In an embodiment, said VFc is no less than 5% or 10% or 20% or 30% or 40% or 50%.
  • VFpl is different from VFp2.
  • said first layer has dual porosities, a material porosity and a layer porosity.
  • the material porosity is in the range of 20-60%, or 30-50%, or 30-40%, or 25-35%. In an embodiment, the material porosity is no less than 25% or 35% or 45%.
  • the ECC has a thickness of no greater than 10 cm or 5 cm or 1 cm. In an embodiment, the ECC a thickness of no greater than 8 mm or 5 mm or 1 mm. In an embodiment, the ECC has a thickness of no greater than 100 microns or 80 microns or 60 microns.
  • the first layer comprises channels and material after (c), wherein contribution to the permeability of the first layer from the channels is greater than contribution to the permeability of the first layer from the material. In an embodiment, no less than 50% or 70% or 90% of the permeability of the first layer is due to the permeability of the channels. In an embodiment, permeability of the material in the first layer is no greater than 50% or no greater than 10% or no greater than 1% or no greater than 0.001% of the permeability of the channels in the first layer.
  • AMM additive manufacturing machine
  • BAM additive manufacturing machine
  • AMM additive manufacturing machine
  • second material to the AMM
  • mixing the first material and the second material into a mixture and (d) forming said mixture into a part.
  • said first material or second material is a gas, or liquid, or solid, or gel.
  • said additive manufacturing comprises extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition, lamination.
  • said AM comprises direct metal laser sintering (DMLS), selective laser sintering (SLS), selective laser melting (SLM), directed energy deposition (DED), laser metal deposition (LMD), electron beam (EBAM), or metal binder jetting.
  • steps (c) and (d) take place continuously.
  • step (c) comprises varying the ratio of the first material and the second material in the mixture.
  • the ratio of the first material and the second material in the mixture is varied in situ.
  • the ratio of the first material and the second material in the mixture is varied in real time.
  • the ratio of the first material and the second material in the mixture is varied continuously.
  • the ratio of the first material and the second material in the mixture is varied according to a composition profile.
  • the ratio of the first material and the second material in the mixture is varied according to a manual algorithm, a computational algorithm, or a combination thereof.
  • the ratio of the first material and the second material in the mixture is varied by controlling material flow rates or pumping rates.
  • step (d) comprises placing said mixture in a pattern on a substrate. In an embodiment, step (d) comprises placing said mixture according to pre-defined specifications.
  • the formed part has varying properties.
  • the properties comprise strength, weight, density, electrical performance, electrochemical performance, or combinations thereof.
  • he formed part possesses superior properties, such as strength, density, weight, electrical performance, or electrochemical performance, or combinations thereof, when compared with a similar part formed by a different process.
  • step (d) comprises depositing said mixture on a substrate.
  • mixing takes place prior to deposition, during deposition, or after deposition.
  • mixing takes place in the AMM or in the air or on the substrate.
  • mixing takes place via advection, dispersion, diffusion, melting, fusion, pumping, stirring, heating, or combinations thereof.
  • an additive manufacturing machine comprising: (a) a first material source; (b) a second material source; and (c) a mixer configured to mix the first material and the second material into a mixture; wherein said AMM is configured to form said mixture into a part.
  • said first material or second material is a gas, or liquid, or solid, or gel.
  • said AMM is configured to perform extrusion, photopolymerization, powder bed fusion, material jetting, binder jetting, directed energy deposition, or lamination.
  • said AMM is configured to perform direct metal laser sintering (DMLS), selective laser sintering (SLS), selective laser melting (SLM), directed energy deposition (DED), laser metal deposition (LMD), electron beam (EBAM), or metal binder jetting.
  • DMLS direct metal laser sintering
  • SLS selective laser sintering
  • SLM selective laser melting
  • DED directed energy deposition
  • LMD laser metal deposition
  • EBAM electron beam
  • said mixer is configured to mix the first material and the second material continuously while the AMM forms said mixture into a part.
  • said mixer is configured to vary the ratio of the first material and the second material in the mixture.
  • said mixer is configured to vary the ratio of the first material and the second material in the mixture in situ.
  • the mixer may be configured to vary the ratio of the first material and the second material in the mixture in real time.
  • the mixer can be configured to vary the ratio of the first material and the second material in the mixture continuously.
  • the mixer is configured to vary the ratio of the first material and the second material in the mixture according to a composition profile.
  • the mixer is configured to vary the ratio of the first material and the second material in the mixture according to a manual algorithm, a computational algorithm, or a combination thereof. In an embodiment, said mixer is configured to vary the ratio of the first material and the second material in the mixture by controlling material flow rates or pumping rates. [322] In an embodiment, said AMM is configured to place said mixture in a pattern on a substrate. In an embodiment, said AMM is configured to place said mixture according to pre defined specifications.
  • the formed part has varying properties.
  • the properties comprise strength, weight, density, electrical performance, electrochemical performance, or combinations thereof.
  • he formed part possesses superior properties, such as strength, density, weight, electrical performance, or electrochemical performance, or combinations thereof, when compared with a similar part formed using a different apparatus.
  • the AMM is configured to deposit said mixture on a substrate.
  • mixing takes place prior to deposition, during deposition, or after deposition.
  • mixing takes place in the AMM or in the air or on the substrate.
  • mixing takes place via advection, dispersion, diffusion, melting, fusion, pumping, stirring, heating, or combinations thereof.
  • SRT refers to a component of the strain rate tensor.
  • Matching SRTs is contemplated in both heating and cooling processes.
  • a fuel cell or an EC gas producer or an EC compressor or a FT catalyst multiple materials or compositions exist. These different materials or compositions often have different thermal expansion coefficients. As such, the heating or cooling process often causes strain or even cracks in the material.
  • a treating process heating or cooling to match the SRTs of different materials/compositions to reduce, minimize, or even eliminate undesirable effects.
  • a method of making a fuel cell wherein the fuel cell comprises a first composition and a second composition, the method comprising heating the first and second compositions, wherein the first composition has a first SRT and the second composition has a second SRT, such that the difference between the first SRT and the second SRT is no greater than 75% of the first SRT.
  • Fig. 7 graphically illustrates strain rate tensors (SRTs) of a first composition and a second composition as a function of temperature.
  • SRTs strain rate tensors
  • heating is achieved via at least one of the following: conduction, convection or radiation.
  • heating comprises electromagnetic radiation (EMR).
  • EMR electromagnetic radiation
  • EMR comprises one or more of UV light, near ultraviolet light, near infrared light, infrared light, visible light, laser or electron beam.
  • the first composition and the second composition are heated at the same time. In an embodiment, the first composition and the second composition are heated at different times. In an embodiment, the first composition is heated for a first period of time, the second composition is heated for a second period of time, wherein at least a portion of the first period of time overlaps with the second period of time.
  • heating takes places more than once for the first composition, or for the second composition, or for both.
  • the first composition and the second composition are heated at different temperatures.
  • the first composition and the second composition are heated using different means.
  • the first composition and the second composition are heated for different periods of time.
  • heating the first composition causes at least partial heating of the second composition, for example, via conduction.
  • heating causes densification of the first composition, or the second composition, or both.
  • the first composition is heated to achieve partial densification resulting in a modified first SRT; and then the first and second compositions are heated such that the difference between the modified first SRT and the second SRT is no greater than 75% of the first modified SRT.
  • the first composition is heated to achieve partial densification resulting in a modified first SRT
  • the second composition is heated to achieve partial densification resulting in a modified second SRT; and then the first and second compositions are heated such that the difference between the modified first SRT and the second modified SRT is no greater than 75% of the first modified SRT.
  • the fuel cell comprises a third composition having a third SRT.
  • the third composition is heated such that the difference between the first SRT and the third SRT is no greater than 75% of the first SRT. In an embodiment, the third composition is heated to achieve partial densification resulting in a modified third SRT; and then the first and second and third compositions are heated such that the difference between the first SRT and the modified third SRT is no greater than 75% of the first SRT.
  • the first and second and third compositions are heated to achieve partial densification resulting in a modified first SRT, a modified second SRT, and a modified third SRT; and then the first and second and third compositions are heated such that the difference between the modified first SRT and the modified second SRT is no greater than 75% of the modified first SRT and the difference between the modified first SRT and the modified third SRT is no greater than 75% of the modified first SRT.
  • the method produces a crack free electrolyte in the fuel cell.
  • heating is performed in situ. In various embodiments, heating causes sintering or co-sintering or both. In various embodiments, heating takes place for no greater than 30 minutes, or no greater than 30 seconds, or no greater than 30 milliseconds.
  • Fig. 8 illustrates a process flow for forming and heating at least a portion of an object.
  • Process flow 800 comprises forming composition 1 810, heating composition 1 at temperature T1 for time tl, forming composition 2 830, then heating composition 1 and composition 2 simultaneously at temperature T2 for time t2 840, wherein at T2, the difference between SRT of composition 1 and SRT of composition 2 is no greater than 75% of SRT of composition 1.
  • 840 represents heating composition 1 and composition 2 simultaneously at temperature T2 and T2' (for example, using different heating mechanisms) for time t2, wherein at T2 and T2', the difference between SRT of composition 1 and SRT of composition 2 is no greater than 75% of SRT of composition 1.
  • Example 1 Making a fuel cell stack.
  • Example 1 is illustrative of the preferred method of making a fuel cell stack.
  • the method uses an AMM model no. 0012323 from Ceradrop and an EMR model no. 092309423 from Xenon Corp.
  • An interconnect substrate is put down to start the print.
  • an anode layer is made by the AMM.
  • This layer is deposited by the AMM as a slurry A, having the composition as shown in the table below.
  • This layer is allowed to dry by applying heat via an infrared lamp.
  • This anode layer is sintered by irradiating it with an electromagnetic pulse from a xenon flash tube for 1 second.
  • An electrolyte layer is formed on top of the anode layer by the AMM depositing a slurry B, having the composition shown in the table below. This layer is allowed to dry by applying heat via an infrared lamp. This electrolyte layer is sintered by irradiating it with an
  • a cathode layer is formed on top of the electrolyte layer by the AMM depositing a slurry C, having the composition shown in the table below. This layer is allowed to dry by applying heat via an infrared lamp. This cathode layer is sintered by irradiating it with an electromagnetic pulse from a xenon flash tube for 1/2 second.
  • An interconnect layer is formed on top of the cathode layer by the AMM depositing a slurry D, having the composition shown in the table below. This layer is allowed to dry by applying heat via an infrared lamp. This interconnect layer is sintered by irradiating it with an electromagnetic pulse from a xenon flash tube for 30 seconds.
  • [341] Mix 200 ml of ethanol with 30 grams of LSCF powder in a beaker. Centrifuge the mixture and obtain an upper dispersion and a lower dispersion. Extract and deposit the upper dispersion using a 3D printer on a substrate and form a LSCF layer. Use a xenon lamp (10 kW) to irradiate the LSCF layer at a voltage of 400V and a burst frequency of 10 Hz for a total exposure duration of 1,000 ms.
  • [342] Mix 200 ml of ethanol with 30 grams of CGO powder in a beaker. Centrifuge the mixture and obtain an upper dispersion and a lower dispersion. Extract and deposit the upper dispersion using a 3D printer on a substrate and form a CGO layer. Use a xenon lamp (10 kW) to irradiate the CGO layer at a voltage of 400V and a burst frequency of 10 Hz for a total exposure duration of 8,000 ms.
  • Example 4 CGO in water.
  • Fig. 12 is a scanning electron microscopy image (side view) illustrating an electrolyte (YSZ) printed and sintered on an electrode (NiO-YSZ).
  • the scanning electron microscopy image shows the side view of the sintered structures, which demonstrates gas-tight contact between the electrolyte and the electrode, full densification of the electrolyte, and sintered and porous electrode microstructures.
  • Example 7 Fuel cell stack configurations.
  • a 48-Volt fuel cell stack has 69 cells with about 1000 Watts of power output.
  • the fuel cell in this stack has a dimension of about 4 cm x 4 cm in length and width and about 7 cm in height.
  • a 48-Volt fuel cell stack has 69 cells with about 5000 Watts of power output.
  • the fuel cell in this stack has a dimension of about 8.5 cm x 8.5 cm in length and width and about 7 cm in height.
  • Example 8 Channeled Electrodes/Fluid Dispersing Components.
  • Fig. 17 schematically illustrates an example of a half cell in an EC reactor.
  • half cell 1700 comprises interconnect 1701.
  • Interconnect 1701 comprises doped lanthanum chromite.
  • Half cell 1700 comprises anode segments 1702 that are printed on interconnect 1701.
  • the anode segments are composed of NiO-YSZ.
  • Anode segments 1702 are sintered using EMR (see Example 1).
  • Half cell 1700 comprises filler material that is deposited between anode segments 1702.
  • the filler material is polymethyl methacrylate (PMMA).
  • Half cell 1700 includes shields 1704 that are printed on filler materials 1703 that are composed of YSZ.
  • Additional anode material 1706 is printed to cover anode segments 1702 and shields 1704 followed by sintering using EMR.
  • the additional anode material is NiO-YSZ.
  • Electrolyte 1705 is printed on additional anode material 1706 and sintered using EMR.
  • Electrolyte 1705 is YSZ.
  • a barrier layer (not shown) composed of CGO is further printed on the electrolyte and sintered using EMR.
  • a layer of cathode (not shown) composed of LSCF is printed on the CGO barrier and sintered.
  • Cathode segments (not shown) composed of LSCF are printed on this layer and sintered. These segments form valleys and filler PMMA is deposited to fill these valleys (not shown).
  • Shields composed of YSZ are printed on the fillers (not shown). Doped lanthanum chromite is printed to cover the shields and cathode segments and then sintered to form another interconnect (not shown). The fillers are removed by furnace heating and channeled electrodes are produced or fluid dispersing components are formed between electrolyte and interconnect (not shown).

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Abstract

L'invention concerne une électrode destinée à être utilisée dans un réacteur électrochimique et son procédé de fabrication. L'électrode présente une porosité d'électrode et comprend un matériau d'électrode comportant des canaux formés en son sein. La porosité du matériau d'électrode est inférieure à la porosité de l'électrode. Dans le procédé, une électrode est fabriquée en déposant une première composition comprenant un premier matériau d'électrode et un premier agent porogène, le premier agent porogène représentant une première fraction volumique VFp1 de la première composition. Une seconde composition est déposée, celle-ci comprenant un second matériau d'électrode et un second agent porogène. Selon cet aspect, le second agent porogène représente une seconde fraction volumique VFp2. La première composition et la seconde composition forment une première couche de l'électrode. Cette première couche est chauffée de sorte qu'au moins une partie du premier agent porogène et au moins une partie du second agent porogène deviennent des espaces vides dans l'électrode.
PCT/US2019/062879 2018-11-22 2019-11-23 Électrodes à double porosité et procédé de fabrication WO2020107027A1 (fr)

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US16/674,629 US11557784B2 (en) 2018-11-06 2019-11-05 Method of making a fuel cell and treating a component thereof
US16/674,695 2019-11-05
US16/674,580 US20200176803A1 (en) 2018-11-06 2019-11-05 Method of Making Fuel Cells and a Fuel Cell Stack
US16/674,657 US11575142B2 (en) 2018-11-06 2019-11-05 Method and system for making a fuel cell
US16/680,770 US20200156104A1 (en) 2018-11-06 2019-11-12 Manufacturing Method with Particle Size Control
US16/680,770 2019-11-12
US201962934808P 2019-11-13 2019-11-13
US62/934,808 2019-11-13
US16/684,864 US11611097B2 (en) 2018-11-06 2019-11-15 Method of making an electrochemical reactor via sintering inorganic dry particles
US16,684,838 2019-11-15
US16/684,838 US20200144654A1 (en) 2018-11-06 2019-11-15 Compact Electrochemical Reactors
US16/684,864 2019-11-15

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