CN113631502B

CN113631502B - Method for producing hydrogen

Info

Publication number: CN113631502B
Application number: CN202080008648.7A
Authority: CN
Inventors: 马修·达姆森; 尼古拉斯·法兰多斯; 金·达姆森
Original assignee: Global Utilities
Current assignee: Global Utilities
Priority date: 2019-01-11
Filing date: 2020-01-10
Publication date: 2023-12-05
Anticipated expiration: 2040-01-10
Also published as: CN113631502A

Abstract

A method of producing hydrogen comprising: an apparatus is provided for introducing a first stream comprising fuel into the apparatus, introducing a second stream comprising water into the apparatus, reducing the water in the second stream to hydrogen, and extracting hydrogen from the apparatus. The first stream and the second stream are not in contact with each other in the device.

Description

Method for producing hydrogen

Citation of related applications

The application is the following partial continuation applications: U.S. patent application Ser. Nos. 16/707,046, 16/707,066 and 16/707,084, filed on 12 months and 9 days of 2019, are the following partial continuation applications: U.S. patent application Ser. Nos. 16/699,453 and 16/699,461, filed on 11/29 in 2019, are the following partial continuation applications: U.S. patent application Ser. Nos. 16/693,268, 16/693,269, 16/693,270 and 16/693,271, filed 11/23/2019, are the following partial continuation applications: U.S. patent application Ser. Nos. 16/684,838 and 16/684,864, filed 11/15/2019, are the following partial continuation applications: U.S. patent application Ser. No. 16/680,770, filed 11/12 in 2019, is a continuation-in-part application for: U.S. patent application nos. 16/674,580, 16/674,629, 16/674,657, 16/674,695, each of which claims the following benefits under 35 u.s.c.119 (e), all filed on month 11, 2019: the U.S. provisional patent application number 62/756,257 submitted at 11 months of 2018, U.S. provisional patent application number 62/756,264 submitted at 11 months of 2018, U.S. provisional patent application number 62/757,751 submitted at 11 months of 2018, U.S. provisional patent application number 62/758,778 submitted at 11 months of 2018, U.S. provisional patent application number 62/767,413 submitted at 11 months of 2018, U.S. provisional patent application number 62/768,864 submitted at 11 months of 2018, U.S. provisional patent application number 62/771,045 submitted at 24 months of 2018, U.S. provisional patent application number 62/773,071 submitted at 11 months of 2018, U.S. provisional patent application number 62/777,912 submitted at 11 months of 2018, U.S. provisional patent application number 62/7710 submitted at 10 months of 2018, U.S. provisional patent application number 62/777,338 submitted at 11 months of 2018, U.S. provisional patent application number 62/779,62/35 submitted at 11 months of 2018, U.S. provisional patent application number 62/771,35 submitted at 11, 2018, U.S. provisional patent application number 62/35,35 submitted at 11, 2018, and U.S. provisional patent application number 62/35,35 submitted at 11,29,29 submitted at 11, U.S. provisional patent application number 62/797,572 filed on day 28 of 1 in 2019, U.S. provisional patent application number 62/798,344 filed on day 29 of 1 in 2019, U.S. provisional patent application number 62/804,115 filed on day 11 of 2 in 2019, U.S. provisional patent application number 62/805,250 filed on day 13 of 2 in 2019, U.S. provisional patent application number 62/808,644 filed on day 21 in 2 in 2019, U.S. provisional patent application number 62/808,644, the U.S. provisional patent application number 62/809,602 submitted at 2 months of 2019, U.S. provisional patent application number 62/814,695 submitted at 3 months of 2019, U.S. provisional patent application number 62/819,374 submitted at 15 months of 2019, U.S. provisional patent application number 62/819,289 submitted at 3 months of 2019, U.S. provisional patent application number 62/824,229 submitted at 3 months of 2019, U.S. provisional patent application number 62/825,576 submitted at 3 months of 2019, U.S. provisional patent application number 62/827,800 submitted at 4 months of 2019, U.S. provisional patent application number 62/834,531 submitted at 16 months of 2019, U.S. provisional patent application number 62/837,089 submitted at 29 months of 2014, U.S. provisional patent application number 62/840,381 submitted at 7 months of 2019, U.S. provisional patent application number 62/125 submitted at 4 months of 2019, U.S. provisional patent application number 62/823, U.S. provisional patent application number 62/269,269,35 submitted at 4 months of 2019, U.S. provisional patent application number 62/269,269,531 submitted at 4 months of 2019, U.S. provisional patent application number 62/269,531 submitted at 4 months of 2019, U.S. provisional patent application number 62/269,35,35, U.S. provisional patent application number 62,269,35 submitted at 4, U.S. provisional patent application number 62,35,35,35,35,35,35, and 2019, 5,35,etc. provisional patent application number of 2019, 5,35, and 2019, 5, and 2019, which are submitted at 5.S. provisional patent application number of the same.S. provisional patent application number by 2019 patent application number is filed by the same.S. provisional patent application number is submitted at 5, which are filed by the subject matter. U.S. provisional patent application Ser. No. 62/869,322 filed on 7.1.2019, U.S. provisional patent application Ser. No. 62/875,437 filed on 7.17.2019, U.S. provisional patent application Ser. No. 62/877,699 filed on 23.7.2019, U.S. provisional patent application number 62/888,319 submitted by 8 months of 2019, U.S. provisional patent application number 62/895,416 submitted by 3 months of 2019, U.S. provisional patent application number 62/896,466 submitted by 5 months of 2019, U.S. provisional patent application number 62/899,087 submitted by 11 months of 2019, U.S. provisional patent application number 62/904,683 submitted by 24 months of 2019, U.S. provisional patent application number 62/912,626 submitted by 10 months of 2019, U.S. provisional patent application number 62/925,210 submitted by 23 months of 2019, U.S. provisional patent application number 62/927,627 submitted by 29 months of 2019, U.S. provisional patent application number 62/928,326 submitted by 30 months of 2019, U.S. provisional patent application number 62/934,808 submitted by 11 months of 2019, U.S. provisional patent application number 62/939,531 submitted by 22 months of 2019, U.S. provisional patent application number 62/944, U.S. provisional patent application number 62/944,944 submitted by 10 months of 2019, and U.S. provisional patent application number 62/944,944 of 2019.S. provisional patent application number 62/10,944 of 2019. The entire disclosure of each of these listed applications is incorporated herein by reference.

Technical Field

The present invention relates generally to electrochemical reactors. More particularly, the present invention relates to electrochemical reactors for the production of synthesis gas and hydrogen.

Background

Synthesis gas (i.e., synthesis gas) is a mixture consisting essentially of hydrogen, carbon monoxide, and typically carbon dioxide. It is used as an intermediate for the production of various products such as synthetic natural gas, ammonia, methanol, hydrogen, synthetic fuels, synthetic lubricants. Synthesis gas can be produced from virtually any hydrocarbon feedstock, such as natural gas, coal, biomass, by steam reforming, dry reforming, partial oxidation, or gasification. Synthesis gas is flammable and is often used in internal combustion engines or for electricity production, although its energy density is less than half that of natural gas.

A large amount of hydrogen is required in the petroleum and chemical industries. For example, a large amount of hydrogen is used for fossil fuel upgrading and production of ammonia or methanol or hydrochloric acid. Petrochemical plants require hydrogen for hydrocracking, hydrodesulfurization, and hydrodealkylation. Hydrogen is also required for hydrogenation processes that increase the saturation level of unsaturated fats and oils. Hydrogen is also a reducing agent for metal ores. Hydrogen may be produced from electrolysis of water, steam reforming, laboratory scale metal-acid processes, thermochemical processes, or anoxic corrosion. Many countries aim at the economies of hydrogen.

Clearly, there remains a need and interest in developing methods and systems for producing these important gases.

Disclosure of Invention

Other aspects and embodiments are provided in the following figures, detailed description, and claims. Features as described herein are combinable and all such combinations are within the scope of the present disclosure unless specifically stated otherwise.

One aspect of the invention is a method of producing hydrogen comprising providing a device, introducing a first stream (first stream) comprising fuel into the device, introducing a second stream (second stream) comprising water into the device, reducing water in the second stream to hydrogen, and extracting hydrogen from the device. The first stream and the second stream are not in contact with each other in the device.

In another method aspect, the first stream is not contacted with hydrogen.

In another method aspect, the first stream and the second stream are separated in the device by an electrolyte.

In other method aspects, the electrolyte is oxygen ion conductive (oxide ion conducting, oxide ion conductive, oxygen ion conductive) and is solid.

In still further method aspects, the electrolyte comprises doped ceria or wherein the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof and a material selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and a combination thereof. Lanthanum chromite includes undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, lanthanum calcium chromite (lanthanum calcium chromite, calcium lanthanum chromite), or combinations thereof. The conductive metal comprises Ni, cu, ag, au or a combination thereof.

In still further method aspects, the electrolyte also conducts electrons and wherein the device does not include interconnects.

In another method aspect, the device is tubular.

In yet another method aspect, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof.

In still other process aspects, the second stream comprises hydrogen.

In still other process aspects, the first stream further comprises water or carbon dioxide.

In yet another method aspect of the invention, the first stream comprises fuel with little to no (with little to no, little) water.

In another method aspect, the device is planar.

In yet another method aspect, an apparatus includes a plurality of repeating units separated by interconnects. Each repeating unit comprises two electrodes with an electrolyte between the electrodes.

In still other method aspects, the electrode includes a fluid channel or fluid dispersion assembly (fluid dispersing component) and the interconnect does not include a fluid dispersion element (fluid dispersing element).

In still other process aspects, a method of producing hydrogen includes introducing a first stream into a reformer prior to the first stream entering a device.

In yet another method aspect of the invention, the reformer is a steam reformer or an autothermal reformer.

In still other process aspects, the method of producing hydrogen comprises operating the apparatus at a temperature of not less than 500 ℃.

In another method aspect, an apparatus includes a first electrode and a second electrode separated by an electrolyte. The first electrode or the second electrode includes Ni or NiO and a material selected from the group consisting of YSZ, CGO, SDC, SSZ, LSGM and combinations thereof.

In yet another method aspect, an apparatus includes a first electrode and a second electrode separated by an electrolyte. The first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Pt, pd, ru, rh, stainless steel and combinations thereof.

In still other method aspects, the first electrode comprises a catalyst.

Drawings

The following figures are provided to illustrate certain embodiments described herein. The drawings are merely illustrative and are not intended to limit the scope of the claimed invention and are not intended to show every possible feature or embodiment of the claimed invention. The figures are not necessarily to scale; in some cases, certain elements of the drawings may be exaggerated relative to other elements of the drawings for illustrative purposes.

Fig. 1A shows an Electrochemical (EC) gas generator according to an embodiment of the present disclosure.

Fig. 1B shows an EC gas generator according to an embodiment of the present disclosure.

Fig. 2A shows a tubular EC gas generator according to an embodiment of the present disclosure.

Fig. 2B shows a cross section of a tubular EC gas generator according to an embodiment of the present disclosure.

FIG. 3A shows a cross section of a multi-tubular EC gas generator according to an embodiment of the disclosure;

FIG. 3B shows a cross section of a multi-tubular EC gas generator according to an embodiment of the disclosure;

FIG. 3C shows a cross section of a multi-tubular EC gas generator according to an embodiment of the disclosure;

FIG. 3D shows a cross section of an EC gas generator according to an embodiment of the present disclosure;

FIG. 4A illustrates a portion of a method of producing an EC gas generator using a single point EMR source, according to an embodiment of the present disclosure.

Fig. 4B illustrates a portion of a method of producing an EC gas generator using a ring light EMR source, according to an embodiment of the disclosure.

FIG. 4C illustrates a portion of a method of producing an EC gas generator using a single point EMR source, according to an embodiment of the disclosure.

FIG. 4D illustrates a portion of a method of producing an EC gas generator using a tubular EMR source, according to an embodiment of the disclosure;

fig. 5A shows a first step in a casting process (tape casting method, casting process) for forming a tubular or multi-tubular EC gas generator, according to an embodiment of the present disclosure;

FIG. 5B shows steps 2-4 in a cast molding process for forming a tubular or multi-tubular EC gas generator, in accordance with embodiments of the present disclosure;

FIG. 6A shows an example of a hydrogen production system 600 without an external heat source, in accordance with an embodiment of the present disclosure;

FIG. 6B shows an alternative hydrogen production system without an external heat source, in accordance with an embodiment of the present disclosure;

fig. 7 shows a fuel cell assembly according to an embodiment of the present disclosure;

fig. 8 schematically shows two fuel cells in a fuel cell stack according to an embodiment of the present disclosure;

fig. 9A shows a perspective view of a fuel cell cartridge (fuel cell cartridge) (FCC) in accordance with an embodiment of the disclosure;

fig. 9B shows a perspective view of a cross section of a Fuel Cell Cartridge (FCC) in accordance with an embodiment of the disclosure;

fig. 9C shows a cross-sectional view of a Fuel Cell Cartridge (FCC) in accordance with an embodiment of the disclosure;

Fig. 9D shows top and bottom views of a Fuel Cell Cartridge (FCC) according to an embodiment of the disclosure;

fig. 10A shows a cross-sectional view of a TFC in accordance with an embodiment of the present disclosure;

fig. 10B shows a cross-sectional view of a TFC in accordance with an embodiment of the present disclosure;

fig. 10C shows a cross-sectional view of a TFC in accordance with an embodiment of the present disclosure;

fig. 11A shows a cross-sectional view of a TFC including a support (support) in accordance with an embodiment of the disclosure;

fig. 11B shows a cross-sectional view of a TFC including a support according to an embodiment of the disclosure;

fig. 11C shows a cross-sectional view of a TFC including a support according to an embodiment of the disclosure;

fig. 12A shows an impermeable interconnect 1202 having a fluid dispersion assembly 1204, according to an embodiment of the present disclosure;

fig. 12B shows an impermeable interconnect 1202 having two fluid dispersion assemblies 1204, according to an embodiment of the disclosure;

fig. 12C shows a segmented fluid dispersion assembly (segmented fluid dispersing component) 1204 having a similar shape but a different size on an impermeable interconnect 1202 in accordance with an embodiment of the present disclosure;

fig. 12D shows a segmented fluid dispersion assembly 1204 having a similar shape and similar dimensions on an impermeable interconnect 1202, in accordance with an embodiment of the present disclosure;

Fig. 12E shows a segmented fluid dispersion assembly 1204 having a similar shape and similar size but closely packed (closed packed) on an impermeable interconnect 1202 in accordance with an embodiment of the present disclosure;

fig. 12F shows segmented fluid dispersion assembly 1204 having different shapes and different sizes on impermeable interconnect 1202, in accordance with an embodiment of the present disclosure;

fig. 12G shows an impermeable interconnect 1202 and a fluid dispersion assembly segment (fluid dispersing component segment) 1204, according to an embodiment of the disclosure;

FIG. 12H illustrates an impermeable interconnect and fluid dispersion assembly segment, according to an embodiment of the present disclosure;

FIG. 12I illustrates an impermeable interconnect and fluid dispersion assembly segment, according to an embodiment of the present disclosure;

fig. 12J shows an impermeable interconnect 1202 and a fluid dispersion assembly segment 1204, in accordance with an embodiment of the present disclosure;

fig. 12K shows a fluid dispersion assembly 1204 according to an embodiment of the disclosure;

FIG. 13A shows a template 1300 for fabricating a channeled electrode according to embodiments of the disclosure;

fig. 13B is a cross-sectional view of a half-cell positioned between a first interconnect and an electrolyte, in accordance with an embodiment of the present disclosure;

Fig. 13C is a cross-sectional view of a half-cell positioned between a second interconnect and an electrolyte, in accordance with an embodiment of the present disclosure;

fig. 13D is a cross-sectional view of a half-cell positioned between a first interconnect and an electrolyte, in accordance with an embodiment of the present disclosure;

fig. 13E is a cross-sectional view of a half-cell positioned between a second interconnect and an electrolyte, in accordance with an embodiment of the present disclosure;

FIG. 14A schematically illustrates a number of segments of a fluid dispersion assembly in a first layer, according to an embodiment of the disclosure;

FIG. 14B schematically illustrates a fluid dispersion assembly in a first layer and a second layer, in accordance with an embodiment of the disclosure;

FIG. 14C schematically illustrates a fluid dispersion assembly in a first layer and second and third layers, in accordance with an embodiment of the present disclosure;

FIG. 14D schematically illustrates a fluid dispersion assembly in a first layer and a second layer, in accordance with an embodiment of the present disclosure;

FIG. 15 is an illustrative example of an electrode having dual porosity in accordance with an embodiment of the present disclosure;

fig. 16 shows a system for integrated deposition (integrated deposition) and heating using electromagnetic radiation (EMR) in accordance with an embodiment of the disclosure;

FIG. 17 is a scanning electron microscope image; and

fig. 18 schematically shows an example of half-cells in an EC reactor.

Detailed Description

SUMMARY

Embodiments of the methods, materials, and processes described herein are directed to electrochemical reactors. The electrochemical reactor includes a solid oxide fuel cell, a solid oxide fuel cell stack, an electrochemical gas generator, an electrochemical compressor, a solid state cell, or a solid oxide flow cell (solid oxide flow battery).

Electrochemical gas generators may be used to produce synthesis gas, hydrogen or other gases for use as fuel or feedstock for fuel cells, for ammonia production, fertilizer production, hydrogenation reactions, bosch reactions, or other applications. The disclosure herein describes a method for producing hydrogen using a device. The device may be an electrochemical gas generator and may be planar or tubular in shape.

Definition of the definition

The following description enumerates several aspects and embodiments of the invention disclosed herein. The specific embodiments are not intended to limit the scope of the invention. However, embodiments provide non-limiting examples of a variety of compositions and methods that are included within the scope of the claimed invention. The description will be read from the perspective of one of ordinary skill in the art. Thus, it is not necessary to include information well known to those of ordinary skill.

Unless otherwise provided herein, the following terms and phrases have the meanings indicated below. The present disclosure may use other terms and phrases not explicitly defined herein. These other terms and phrases should have the meaning that they would have within the context of this disclosure to those of ordinary skill in the art. In some cases, terms or phrases may be defined in the singular or in the plural. In these instances, it is to be understood that any term in the singular may include its plural counterpart and vice versa, unless explicitly indicated to the contrary.

As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to "a substitute" encompasses a single substitute as well as two or more substitutes and the like. As used herein, "for example," "such as," or "including" means introducing examples that further clarify more general subject matter. These examples are provided solely as an aid in understanding the embodiments described in this disclosure and are not meant to be limiting in any way unless explicitly indicated otherwise. Nor does these phrases indicate any kind of preference for the disclosed embodiments.

As used herein, compositions and materials are used interchangeably unless otherwise indicated. Each composition/material may have a variety of elements, phases, and components. As used herein, heating refers to actively adding energy to a composition or material.

The term "in situ" in this disclosure refers to a process of treating (e.g., heating) in the same location or in the same apparatus as the process of forming the composition or material. For example, the deposition process and the heating process are performed at the same device and at the same location, in other words, the device is not changed and the location within the device is not changed. For example, the deposition process and the heating process are performed at different locations in the same apparatus, which is also considered to be in situ.

In the present disclosure, a major face of an object is the face of the object having a surface area greater than the average surface area of the object, where the average surface area of the object is the total surface area of the object divided by the number of faces of the object. In some cases, a major surface refers to the face of an object or body having a surface area greater than the minor surface. In the case of a flat fuel cell or a non-SIS fuel cell, the major face is a lateral face or surface.

As used herein, lateral refers to a direction perpendicular to the stacking direction of layers in a non-SIS fuel cell. Thus, the lateral direction refers to a direction perpendicular to the stacking direction of the layers in the fuel cell or the stacking direction of the sheets (slices) forming the object during deposition. Transverse also refers to the direction of diffusion of the deposition process.

In the present disclosure, a liquid precursor of a substance refers to a dissolved form, such as a salt in an aqueous solution, containing the substance. For example, copper salts dissolved in aqueous solutions are considered liquid precursors of copper. Copper particles suspended/dispersed (non-dissolved) in a liquid are not considered to be liquid precursors of copper.

As used herein CGO refers to gadolinium doped ceria, alternatively also known as gadolinium oxide doped ceria, gadolinium doped ceria (IV), GDC or GCO (formula Gd: ceO ₂ ). Unless otherwise indicated, CGO and GDC are used interchangeably.

In this disclosure, synthesis gas (i.e., synthesis gas) refers to a mixture consisting essentially of hydrogen, carbon monoxide, and carbon dioxide.

In the present disclosure, absorbance is a measure of a substance's ability to absorb electromagnetic radiation (EMR) at a wavelength. Radiation absorption refers to the energy absorbed by a substance when exposed to radiation.

As used herein, ceria refers to cerium oxide (cerium oxide), also known as cerium oxide (ceric oxide), cerium oxide (ceric dioxide), or cerium oxide (ceric dioxide), which is an oxide of rare earth metal cerium. Doped ceria refers to ceria doped with other elements such as Samaria Doped Ceria (SDC) or gadolinium doped ceria (GDC or CGO).

As used herein, chromite refers to chromium oxide, which includes all oxidation states of chromium oxide.

As used herein, "having little to no water" means having a water content of no more than 1 g/m ³ Or not more than 200 mg/m ³ Or not more than 50 mg/m ³ 。

Interconnects in electrochemical devices (e.g., fuel cells) are typically metallic or ceramic, which are disposed between individual cells or repeating units. The purpose of this is to connect each cell or repeating unit so that the electricity can be distributed or combined. The interconnect is also referred to as a bipolar plate in an electrochemical device. An interconnect as an impermeable layer as used herein refers to a layer that is impermeable to fluid flow. For example, the impermeable layer has a permeability of less than 1 micro darcy, or less than 1 nano darcy.

In this disclosure, an interconnect without a fluid dispersion element refers to an interconnect without an element (e.g., channel) that disperses a fluid. The fluid may comprise a gas or a liquid or a mixture of gas and liquid. These fluids may include one or more of hydrogen, methane, ethane, propane, butane, oxygen, ambient air, or light hydrocarbons (i.e., pentane, hexane, octane). Such interconnects may have inlets and outlets (i.e., openings) for the passage of material or fluid.

In this disclosure, the term "microchannel" is used interchangeably with microfluidic channel or microfluidic flow channel.

In the present disclosure, sintering refers to a method of forming a solid block of a material by heat or pressure or a combination thereof, without melting the material to the extent of liquefying. For example, the particles of material are agglomerated into a solid or porous mass by heating, wherein atoms in the particles of material diffuse across the particle boundaries, thereby causing the particles to fuse together and form a solid piece. In the present disclosure and appended claims, T _Sintering Refers to the temperature at which this phenomenon begins to occur.

As used herein, the term "pore former" is intended to have a relatively broad meaning. "pore former" may refer to any particulate material contained in the composition during formation, which may be partially or completely free of space by methods such as heating, combustion or evaporation. As used herein, the term "conductive component" is intended to mean components in a fuel cell that are conductive, such as electrodes and interconnects.

For illustrative purposes, the production of Solid Oxide Fuel Cells (SOFCs) will be used herein as an example system describing various embodiments. As will be appreciated by those skilled in the art, the methods and production methods described herein are applicable to any electrochemical device, reactor, vessel, catalyst, etc. Examples of electrochemical devices or reactors include Electrochemical (EC) gas generators, electrochemical (EC) compressors, solid oxide fuel cells, solid oxide fuel cell stacks, solid state cells, or solid oxide stream cells (solid oxide flow battery). In one embodiment, the electrochemical reactor comprises a solid oxide fuel cell, a solid oxide fuel cell stack, an electrochemical gas generator, an electrochemical compressor, a solid state cell, or a solid oxide flow cell (solid oxide flow battery). The catalyst comprises a Fischer Tropsch (FT) catalyst or a reformer catalyst. The reactor/vessel comprises an FT reactor or a heat exchanger.

Electrochemical (EC) gas generator

Fig. 1A shows an Electrochemical (EC) gas generator 100 according to an embodiment of the present disclosure. The EC gas generator device 100 comprises a first electrode 101, an electrolyte 103 and a second electrode 102. The first electrode 101 is configured to receive fuel and not receive oxygen (oxygen) 104. The second electrode 102 is configured to receive water or nothing as indicated by arrow 105. The apparatus 100 is configured to simultaneously produce hydrogen 107 from the second electrode 102 and synthesis gas 106 from the first electrode 101. In one embodiment, 104 represents methane and water or methane and carbon dioxide entering the apparatus 100. In other embodiments, 103 represents an oxygen ion conducting membrane (oxide ion conducting membrane ). In one embodiment, the first electrode 101 and the second electrode 102 may include Ni-YSZ or NiO-YSZ. Arrow 104 represents a hydrocarbonAnd water or hydrocarbon and carbon dioxide inflow. Arrow 105 represents the inflow of water or water and hydrogen. In some embodiments, the electrode 101 comprises Cu-CGO, which further optionally comprises CuO or Cu ₂ O or a combination thereof. Electrode 102 comprises Ni-YSZ or NiO-YSZ. Arrow 104 represents the inflow of hydrocarbons with little to no water, no carbon dioxide, and no oxygen, and 105 represents the inflow of water or water and hydrogen. Since water provides the oxygen ions (which are transported through the electrolyte) required to oxidize the hydrocarbon/fuel at the opposite electrode, water is considered an oxidant in this case.

Fig. 1B shows an EC gas generator 110 according to an embodiment of the present disclosure. The EC gas generator device 110 comprises a first electrode 111, a second electrode 112 and an electrolyte 113 located between the electrodes. The first electrode 111 is configured to receive fuel and not receive oxygen 104, wherein the second electrode 112 is configured to receive water or nothing. In some embodiments, 113 represents a proton conducting membrane (proton conducting membrane ), and 111 and 112 represent Ni-barium zirconate electrodes. Hydrogen 107 is produced from the second electrode 112 and synthesis gas 106 is produced from the first electrode 111.

In the present disclosure, oxygen-free means that no oxygen or at least insufficient oxygen is present at the first electrode 101, 111 to interfere with the reaction. In addition, in the present disclosure, water means only that the predetermined raw material is water and does not exclude trace elements or inherent components in the water. For example, water containing salts or ions is considered to be in the range of water alone. Only water does not require 100% pure water either, but this embodiment is included. In an embodiment, the hydrogen gas generated from the second electrode 102, 112 is pure hydrogen, which means that hydrogen is the main component in the gas phase generated from the second electrode. In some cases, the hydrogen content is not less than 99.5%. In some cases, the hydrogen content is not less than 99.9%. In some cases, the hydrogen gas produced from the second electrode is the same purity as that produced from electrolysis of water.

In one embodiment, the first electrode 101, 111 is configured to receive methane and water or methane and carbon dioxide. In one embodiment, the fuel comprises hydrocarbons 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. In one embodiment, the device does not generate electricity. In one embodiment, the apparatus includes a mixer configured to receive at least a portion of the first electrode product and at least a portion of the second electrode product. The mixer may be configured to produce a gas stream wherein the ratio of hydrogen to carbon oxides is not less than 2, or not less than 3, or between 2 and 3.

In one embodiment, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In one embodiment, the catalyst comprises nickel oxide, silver, cobalt, cesium, nickel, iron, manganese, nitrogen, tetra-nitrogen (tetra-nitrogen), molybdenum, copper, chromium, rhodium, ruthenium, palladium, osmium, iridium, or platinum, or combinations thereof. In one embodiment, the substrate comprises gadolinium, ceO ₂ 、ZrO ₂ 、SiO ₂ 、TiO ₂ Steel, cordierite (2 MgO-2 Al) ₂ O ₃ -5SiO ₂ ) Aluminum titanate (Al) ₂ TiO ₅ ) Silicon carbide (SiC), all phases of alumina, yttria or scandia stabilized zirconia (YSZ), gadolinium oxide or samaria doped ceria, or combinations thereof. In some embodiments, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise an accelerator, wherein the accelerator is selected from the group consisting of Mo, W, ba, K, mg, fe and combinations thereof. In one embodiment, the anode (e.g., the first electrode or the second electrode) comprises a catalyst, wherein the catalyst is selected from the group consisting of nickel, iron, palladium, platinum, ruthenium, rhodium, cobalt, and combinations thereof.

In some embodiments, the electrode and the electrolyte form a repeating unit. The device may comprise two or more repeating units separated by an interconnect. In a preferred embodiment, the interconnect does not contain a fluid dispersion element. In one embodiment, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise a fluid channel. Alternatively, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise a fluid dispersion assembly.

Also discussed herein are assembly methods that include forming a first electrode 101, 111, forming a second electrode 102, 112, and forming an electrolyte 103, 113 located between the electrodes, wherein the electrodes and electrolyte are assembled as they were formed. The forming may include material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, slot photopolymerization (vat photopolymerization), powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or combinations thereof. The electrode and the electrolyte may form a repeating unit. The method may further include forming two or more repeating units and forming an interconnect between the two or more repeating units. The assembly method may further include forming a fluid channel or fluid dispersion assembly in the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112. The forming method may include in situ heating. In a preferred embodiment, the heating includes EMR. The EMR may include one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, or an electron beam.

The first electrode 101, 111 is configured to receive fuel and not to receive oxygen, wherein the second electrode 102, 112 is configured to receive only water or nothing, wherein the device is configured to simultaneously produce hydrogen from the second electrode 102, 112 and syngas from the first electrode 101, 111.

Further discussed herein are methods that include providing a device comprising a first electrode 101, 111, a second electrode 102, 112, and an electrolyte 103, 113 positioned between the electrodes, introducing an oxygen-free fuel into the first electrode 101, 111, introducing only water or no substance into the second electrode 102, 112 to produce hydrogen, extracting hydrogen from the second electrode 102, 112, and extracting synthesis gas from the first electrode 101, 111. In a preferred embodiment, the fuel comprises methane and water or methane and carbon dioxide. In a preferred embodiment, the fuel comprises hydrocarbons having a carbon number in the range of 1-12 or 1-10 or 1-8.

In one embodiment, the process comprises feeding at least a portion of the extracted synthesis gas to a fischer-tropsch reactor. In one embodiment, the process comprises feeding at least a portion of the extracted hydrogen to a fischer-tropsch reactor. In one embodiment, at least a portion of the extracted synthesis gas and at least a portion of the extracted hydrogen are adjusted such that the ratio of hydrogen to carbon oxides is not less than 2, or not less than 3, or between 2 and 3.

In one embodiment, the fuel is introduced directly to the first electrode 101, 111, or the water is introduced directly to the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112. In one embodiment, the first electrode 101, 111 or the second electrode 102, 112, or both the first electrode 101, 111 and the second electrode 102, 112, comprise a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In preferred embodiments, the catalyst comprises nickel oxide, silver, cobalt, cesium, nickel, iron, manganese, nitrogen, tetranitrogen, molybdenum, copper, chromium, rhodium, ruthenium, palladium, osmium, iridium, platinum, or combinations thereof. In a preferred embodiment, the substrate comprises gadolinium, ceO ₂ 、ZrO ₂ 、SiO ₂ 、TiO ₂ Steel, cordierite (2 MgO-2 Al) ₂ O ₃ -5SiO ₂ ) Aluminum titanate (Al) ₂ TiO ₅ ) Silicon carbide (SiC), all phases of alumina, yttria or scandia stabilized zirconia (YSZ), gadolinium oxide or samaria doped ceria, or combinations thereof.

In one embodiment, the method comprises applying a potential difference between the first electrode 101, 111 and the second electrode 102, 112. In one embodiment, the method comprises using the extracted hydrogen in one or a combination of the following reactions: fischer-tropsch (FT) reactions, dry reforming reactions, sabatier reactions catalyzed by nickel, bosch reactions, reverse water gas shift reactions, electrochemical reactions to generate electricity, production of ammonia and/or fertilizer, electrochemical compressors for hydrogen storage or hydrogen vehicle fueling, or hydrogenation reactions.

In various embodiments, the gas generator is not a fuel cell and does not generate electricity. In some cases, electricity may be applied to the gas generator at the anode and cathode. In other cases, no electricity is needed.

Disclosed herein are devices comprising a first electrode, a second electrode, and an electrolyte located between the electrodes, wherein when the device is in use, the first electrode and the second electrode comprise a metal phase free of platinum group metals, and wherein the electrolyte is oxygen ion conductive. In one embodiment, wherein the first electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samaria Doped Ceria (SDC), scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. In one embodiment, the first electrode is configured to receive fuel and water or fuel and carbon dioxide. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof.

In one embodiment, the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu O, ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel, and combinations thereof. In one embodiment, the first electrode is configured to receive fuel with little to no water. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the second electrode comprises Ni or NiO and a material selected from the group consisting of Yttria Stabilized Zirconia (YSZ), cerium Gadolinium Oxide (CGO), samarium oxide doped ceria (SDC), scandia Stabilized Zirconia (SSZ), strontium magnesium doped lanthanum gallate (lanthanum strontium gallate magnesite) (LSGM), and combinations thereof. In one embodiment, the second electrode is configured to receive water and hydrogen and is configured to reduce the water to hydrogen. In one embodiment, the electrolyte comprises doped twoThe cerium oxide or a material in which the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and combinations thereof. In one embodiment, the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, lanthanum calcium chromite, or a combination thereof. In one embodiment, the conductive metal comprises Ni, cu, ag, au or a combination thereof.

In one embodiment, the first electrode 101, 111 or the second electrode 102, 112 or both the first electrode 101, 111 and the second electrode 102, 112 comprise a fluid channel. Alternatively, the first electrode 101, 111 or the second electrode 102, 112 or both the first electrode 101, 111 and the second electrode 102, 112 comprise a fluid dispersion component. In one embodiment, the electrode and electrolyte 103, 113 form a repeating unit and wherein the device comprises a plurality of repeating units separated by interconnects. In one embodiment, the interconnect does not contain a fluid dispersion element. In one embodiment, the electrodes 101, 102, 111, 112 and the electrolytes 103, 113 may be planar. The fluid dispersion assembly or fluid channel in the electrode functions to distribute a fluid, e.g., a reactive gas (e.g., methane, hydrogen, carbon monoxide, air, oxygen, steam, etc.) in the electrochemical reactor. As such, conventional interconnects with vias are no longer required. The design and production of these conventional interconnects with channels is complex and expensive. According to the present disclosure, the interconnect is simply an impermeable layer that conducts or collects electrons, without fluid dispersion elements.

In one embodiment, the device does not include an interconnect. In one embodiment, the electrolytes 103, 113 conduct oxygen ions and electrons. In one embodiment, the electrodes 101, 102, 111, 112 and the electrolytes 103, 113 are tubular. In some embodiments, the electrochemical reactions at the anode and cathode are spontaneous without applying an electrical potential/current to the reactor. In these cases, no interconnects are required, which significantly simplifies the device. In these cases, the electrolyte in the device conducts both oxygen ions and electrons.

In one embodiment, the device comprises a reformer upstream of the first electrode 101, 111, wherein the first electrode 101, 111 comprises Ni or NiO or a combination thereof. In one embodiment, the reformer is a steam reformer or an autothermal reformer. In one embodiment, the device is configured to operate at a temperature of not less than 500 ℃, or not less than 600 ℃, or not less than 700 ℃.

In one embodiment, the electrode and electrolyte are tubular, wherein the first electrode is the outermost layer and the second electrode is the innermost layer, wherein the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel, and combinations thereof. In one embodiment, the electrodes and electrolyte are tubular, with the first electrode being the outermost layer and the second electrode being the innermost layer, with the second electrode being configured to receive water and hydrogen.

Also disclosed herein is a device comprising a first electrode, a second electrode, and an electrolyte positioned between the electrodes, wherein the first electrode comprises doped lanthanum chromium oxide (lanthanum chromium oxide ) and doped or undoped ceria, wherein the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), scandium oxide stabilized zirconia (SSZ), LSGM, ceria, and combinations thereof, and wherein the electrolyte is oxygen ion conductive. In one embodiment, the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, or a combination thereof. In one embodiment, the device is planar. In one embodiment, the device is tubular.

Further discussed herein are methods of making a device comprising forming a first electrode, forming a second electrode, and forming an electrolyte positioned between the electrodes, wherein the first electrode comprises doped lanthanum chromium oxide and doped or undoped ceria, wherein the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), scandium oxide stabilized zirconia (SSZ), LSGM, ceria, and combinations thereof, and wherein the electrolyte is oxygen ion conductive. In one embodiment, the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, or a combination thereof. In one embodiment, the forming comprises material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, slot photopolymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, or ultrasonic ink jet printing, or a combination thereof. In one embodiment, forming comprises extrusion, dip coating, spray coating, spin coating, brush coating, paste coating, or a combination thereof. In one embodiment, forming includes heating using an electromagnetic radiation source or oven.

Methods of making devices are discussed herein that include forming a first electrode, forming a second electrode, and forming an electrolyte positioned between the electrodes, wherein when the device is in use, the first electrode and the second electrode comprise a metal phase that is free of platinum group metals, and wherein the electrolyte is oxygen ion conductive. In one embodiment, the electrodes and electrolyte are assembled as they are formed. In one embodiment, the electrode and electrolyte form a repeating unit and the method includes forming the plurality of repeating units and forming an interconnect between the repeating units. In one embodiment, the interconnect does not contain a fluid dispersion element. In one embodiment, the method includes forming a fluid channel or a fluid dispersion assembly in the first electrode or the second electrode or both the first electrode and the second electrode.

In one embodiment, the first electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samaria Doped Ceria (SDC), scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. In one embodiment, the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel, and combinations thereof. In one embodiment, the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samaria Doped Ceria (SDC), scandia Stabilized Zirconia (SSZ), LSGM, ceria, and combinations thereof. In one embodiment of the present invention, in one embodiment,the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, or a combination thereof.

In one embodiment, forming comprises material jetting, binder jetting, ink jet printing, aerosol jetting, aerosol jet printing, slot photopolymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic ink jet printing, or combinations thereof. In one embodiment, the method includes in situ heating. In one embodiment, the heating includes electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, or a combination thereof. In one embodiment, the EMR is provided by a xenon lamp. In one embodiment, the electrodes and electrolyte are planar. In one embodiment, the device does not include an interconnect. In one embodiment, the electrolyte conducts oxygen ions and electrons.

In one embodiment, forming includes a) depositing a composition on a substrate to form a sheet; b) Drying the sheet using a non-contact dryer; c) The sheet is heated using electromagnetic radiation (EMR) or conduction or both. In one embodiment, the method includes repeating steps a) -c) to generate the device piece-by-piece (slice). In one embodiment, the method includes d) measuring the temperature T of the patch without contacting the patch for a time T after the last EMR exposure, where T is no greater than 5 seconds, or no greater than 4 seconds, or no greater than 3 seconds, no greater than 2 seconds, or no greater than 1 second. In one embodiment, the method comprises e) combining T with T _Sintering In comparison, wherein if the composition is nonmetallic, T _Sintering Not less than 45% of the melting point of the composition; or wherein if the composition is metallic, T _Sintering Not less than 60% of the melting point of the composition. In one embodiment, the method comprises e) combining T with T _Sintering In comparison, wherein T was previously determined by correlating the measured temperature with a microstructure image of the sheet, a scratch test of the sheet, an electrochemical performance test of the sheet, an expansion method measurement of the sheet, a conductivity measurement of the sheet, or a combination thereof _Sintering . In one embodiment, the methodIncluding if T is less than T _Sintering 90% of the total, then the sheet is heated in the second stage using EMR or conduction or both.

In one embodiment, the drying is performed for a period of time within the following ranges: no more than 5 minutes, or no more than 3 minutes, or no more than 1 minute, or 1 s to 30 s, or 3 s to 10 s. In one embodiment, the non-contact dryer includes an infrared heater, a hot air blower, an ultraviolet light source, or a combination thereof.

For example, all layers of the EC gas generator are formed and assembled by printing. The materials used to prepare the anode, cathode, electrolyte, and interconnect are made into ink forms (ink forms) containing solvents and particles (e.g., nanoparticles), respectively. The ink optionally comprises a dispersant, a binder, a plasticizer, a surfactant, a co-solvent, or a combination thereof. For the anode and cathode of the gas generator, the NiO and YSZ particles are mixed with a solvent, where the solvent is water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used. For electrolytes, YSZ particles are mixed with a solvent, where the solvent is water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used. For the interconnect, the metal particles (e.g., silver nanoparticles) are dispersed or suspended in a solvent, where the solvent may include water (e.g., deionized water), an organic solvent (e.g., mono-, di-, or tri-or higher ethylene glycol, propylene glycol, 1, 4-butanediol or ethers of these glycols, thiodiglycol, glycerol and ethers and esters thereof, polyglycerol, mono-, di-, and tri-ethanolamines, propanolamine, 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. For the barrier layer, the CGO particles may be dissolved, dispersed or suspended in a solvent, wherein the solvent is water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used. CGO is used as a barrier to LSCF. YSZ may also be used as a barrier to LSM.

Tubular and multi-tubular EC gas generators

Fig. 2A shows (not to scale) a tubular EC gas generator 200 according to an embodiment of the disclosure. The tubular EC gas generator 200 comprises an inner tubular structure 202, an outer tubular structure 204 and an electrolyte 206 arranged between the inner and outer tubular structures 202, 204, respectively. In some embodiments, the electrolyte 206 may instead comprise a membrane. The tubular gas generator 200 also includes a void space 208 for passage of fluid.

Fig. 2B shows (not to scale) a cross-section of a tubular EC gas generator 200 according to an embodiment of the disclosure. The tubular EC gas generator 200 comprises a first inner tubular structure 202, a second outer tubular structure 204 and an electrolyte 206 located between the inner and outer tubular structures 202, 204. In some embodiments, the electrolyte 206 may be referred to as a membrane. The tubular gas generator 200 also includes a void space 208 for passage of fluid.

In one embodiment, the inner tubular structure 202 contains electrodes. The inner tubular structure 202 may be an anode or a cathode. In one embodiment, the inner tubular structure 202 may be porous. The inner tubular structure 202 may comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. The inner tubular structure 202 may comprise doped or undoped ceria and be selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel, and combinations thereof. In one embodiment, the outer tubular structure 204 comprises an electrode. The outer tubular structure 204 may be an anode or a cathode. The outer tubular structure 204 may comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. The outer tubular structure 204 may comprise doped or undoped ceria and be selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel, and combinations thereof. It should be noted that the above list of materials is not limiting.

In an embodiment, the electrolyte 206 comprises doped ceria or wherein the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof and a material selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and a combination thereof. In one embodiment, the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, lanthanum calcium chromite, or a combination thereof. In one embodiment, the conductive metal comprises Ni, cu, ag, au or a combination thereof. Electrolyte 206 is oxygen ion conductive. In some cases, the electrolyte 206 is oxygen ion conductive and electron conductive (electronically conducting). In some embodiments, generator 200 also includes one or more interconnects.

Fig. 3A shows a cross section of a multi-tubular EC gas generator 300 according to an embodiment of the present disclosure. The EC gas generator 300 comprises an inner electrode 302, an outer electrode 304 and an electrolyte 306 between the electrodes 302, 304. In some embodiments, electrolyte 306 is referred to as a membrane. The inner electrode 302 includes a plurality of tubular void spaces 308 connected in a radial direction. Void space 308 allows fluid to pass. Void space 308 may also be referred to as a flow channel (fluid passage). The multi-tubular structure 300 includes a plurality of flow channels 308 in the axial direction of the tubular structure 300. Void space 308 may be circular-like, oval-like, or other similar shape in cross-section. The cross-section of the space 308 may be irregularly shaped as shown in fig. 3A. The generator 300 has a cross section with a length and a width, wherein the length is at least 2 times the width and the cross section is perpendicular to the axial direction of the tube. The multi-tubular structure 300 is composed of a plurality of individual tubular structures 309 (indicated by dashed lines).

The inner electrode 302 in the generator 300 may have a unitary structure (unitary construction, one-piece construction) and no brazed or welded components. In one embodiment, generator 300 has a unitary structure and has no brazed or welded components. In one embodiment, electrolyte 306 is oxygen ion conductive and is solid. In one embodiment, the electrolyte comprises the materials listed herein previously for electrolyte 206 in tubular reactor 200. In an embodiment, the electrodes 302, 304 may comprise one or more of the materials listed herein previously for the tubular structures 202, 204 in the tubular reactor 200. In some embodiments, generator 300 further comprises one or more interconnects.

Fig. 3B shows a cross section of a multi-tubular EC gas generator 320 according to an embodiment of the present disclosure. The gas generator has a rectangular-like cross-section. The EC gas generator 320 comprises an inner electrode 302, an outer electrode 304, and an electrolyte 306 located between the electrodes 302, 304. In some embodiments, a membrane may be used in place of electrolyte 306. The inner electrode 302 includes a plurality of void spaces 308 connected in a radial direction of the tube-like void spaces 308. Void space 308 allows fluid to pass. The multi-tubular structure 320 includes a plurality of flow channels 308 in an axial direction of the tubular structure 320. The cross-section of void space 308 may be circular-like, oval-like, square-like, hexagonal-like, triangular-like, or other similar shapes in a random or regular fashion. The generator 320 has a cross section with a length and a width, wherein the length is at least 2 times the width and the cross section is perpendicular to the axial direction of the tube.

The inner electrode 302 in the generator 320 may have a unitary structure and have no brazed or welded components. Generator 320 may have a unitary construction and have no brazed or welded components. In one embodiment, electrolyte 306 is oxygen ion conductive. In embodiments, the electrolyte may comprise one or more of the materials listed herein previously for electrolyte 206 in tubular reactor 200. In an embodiment, the electrodes 302, 304 may comprise one or more of the materials listed herein previously for the tubular structures 202, 204 in the tubular reactor 200. In some implementations, the generator 320 also includes one or more interconnects.

Fig. 3C shows a cross section of a multi-tubular EC gas generator 340 according to an embodiment of the present disclosure. The gas generator 340 has a rectangular-like cross section. The EC gas generator 340 includes an inner electrode 302, an outer electrode 304, and an electrolyte 306 positioned between the electrodes 302, 304. In some embodiments, electrolyte 306 is referred to as a membrane. The inner electrode 302 includes a plurality of void spaces 308 connected in the axial direction of the tube. Void space 308 allows fluid to pass. The multi-tubular structure 340 includes a plurality of flow channels 308 in an axial direction of the tubular structure 340. The cross-section of void spaces 308 may be square-like or rectangular-like as shown in fig. 3C or other similar shapes in a regular manner, wherein the cross-sectional area of each void space is substantially the same. The generator 340 has a cross section with a length and a width, wherein the length is at least 2 times the width and the cross section is perpendicular to the axial direction of the tube.

The inner electrode 302 in the generator 340 may have a unitary structure and have no brazed or welded components. Generator 340 may have a unitary construction and have no brazed or welded components. In one embodiment, electrolyte 306 is oxygen ion conductive. In embodiments, the electrolyte may comprise one or more of the materials listed herein previously for electrolyte 206 in tubular reactor 200. In an embodiment, the electrodes 302, 304 may comprise one or more of the materials listed herein previously for the tubular structures 202, 204 in the tubular reactor 200. In some embodiments, generator 340 further comprises one or more interconnects.

Fig. 3D shows a cross section of an EC gas generator 360 according to an embodiment of the present disclosure. The gas generator 360 has a rectangular-like cross-section. The EC gas generator 360 is similar to the gas generator 340 in fig. 3C except that the flow channel 380 is singular, as shown in fig. 3D.

Production of tubular and multi-tubular EC gas generators

Methods of making tubular EC gas generators as shown by devices 200, 300, 320, 340 and 360 are further discussed herein, as are examples of some tubular designs. At least three methods are discussed herein as to how to make the first tube: extrusion, substrate and methods as shown in fig. 5A-5B.

In one embodiment, a method of making a tubular EC gas generator includes forming a first tubular structure by extrusion. In some embodiments, the first tubular structure is an inner electrode 202. The method further includes depositing a layer on the outer cylindrical surface of the first tubular structure 202, wherein the layer includes an electrolyte 206, and depositing the second tubular structure 204 on the electrolyte 206, wherein the electrolyte 206 is oxygen ion conductive. In one embodiment, the first tubular structure 202 and the second tubular structure 204 comprise a metallic phase that is free of platinum group metals when the device is in use. In one embodiment, the device does not contain an interconnect and wherein the electrolyte is electronically conductive.

In another production method embodiment, the method includes extruding an inner tubular structure 202; sintering the inner tubular structure 202 in a furnace or by EMR to form a first electrode; coating the outer surface of the inner tubular structure 202 with an electrolyte material; sintering the electrolyte material in a furnace or EMR to form an electrolyte 206; coating the electrolyte 206 with an electrode material; the electrode material is sintered in an oven or using electromagnetic radiation (EMR) to form the outer tubular structure 204, wherein the outer tubular structure 204 is a second electrode. In one embodiment, the outer tubular structure 204 comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel and combinations thereof; and sintering the outer tubular structure 204 using EMR. In one embodiment, the method further comprises reducing the outer tubular structure 204 or reducing the inner tubular structure 202 or both tubular structures 202, 204. These methods describe the "inside out" method, wherein the first extruded layer is the inner electrode layer.

The following method describes an "outside in" method in which the first layer formed is the outer tubular structure 204 or the outer electrode layer. The method includes extruding an outer tubular structure 204; sintering the outer tubular structure 204 in a furnace or by EMR to form a first electrode; coating the inner surface of the outer tubular structure 204 with an electrolyte material; in ovens or furnaces Sintering the electrolyte material in the EMR to form electrolyte 206; coating the inner surface of the electrolyte 206 with an electrode material; the electrode material is sintered in an oven or using electromagnetic radiation (EMR) to form the inner tubular structure 202, wherein the inner tubular structure 202 is the second electrode. In one embodiment, the inner tubular structure 202 comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel and combinations thereof; and sintering the inner tubular structure 202 using EMR. In one embodiment, the method further comprises reducing the outer tubular structure 204 or reducing the inner tubular structure 202 or both tubular structures 202, 204.

In one embodiment, the coating step for use in the "inside-out" and "outside-in" methods includes dip coating, spray coating, ultrasonic spray coating, spin coating, brush coating, paste coating, or a combination thereof. Electromagnetic radiation includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, microwaves, or combinations thereof. In one embodiment, the electromagnetic radiation is provided by a xenon lamp. In some implementations, an apparatus may include one or more interconnects. In one embodiment, the inner tubular structure 202 and the outer tubular structure 204 contain one or more fluid passages or one or more fluid dispersion components or both fluid passages and fluid dispersion components.

In another embodiment, the inner tubular structure 202 or the outer tubular structure 204 may be formed from particles and not from a liquid precursor, particularly when the inner tubular structure 202 or the outer tubular structure 204 comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel, and combinations thereof. The particles are suspended in a liquid prior to deposition or coating, such as dip coating, spray coating, spin coating, brush coating, paste coating, or a combination thereof. In these cases, the inner tubular structure 202 or the outer tubular structure 204 is sintered using electromagnetic radiation (EMR).

In other embodiments, a first tube-like substrate is provided. The tubular substrate is substantially in the desired shape of the EC gas generator. In a first embodiment, a first electrode material is deposited outside the tubular substrate. The first electrode material is sintered to form the internal electrode 202. Then, an electrolyte material is deposited on the surface of the internal electrode layer 202. The electrolyte material is sintered to form electrolyte 206. Then, a second electrode material is deposited on the electrolyte 206. Then, the second electrode material is sintered to form the external electrode 204. The method may be described as an "inside-out substrate method" in which the first layer formed on the substrate is the inner electrode layer 202, then the electrolyte 206 layer, and then the outer electrode layer 204. The first and second electrodes may be anodes or cathodes. Sintering may include heating or EMR sintering.

In another similar method, a tube-like substrate is provided. A first electrode material is deposited inside the tubular substrate. The first electrode material is sintered to form the external electrode 204. Then, an electrolyte material is deposited on the surface of the external electrode layer 204. The electrolyte material is sintered to form electrolyte 206. Then, a second electrode material is deposited on the electrolyte 206. The second electrode material is then sintered to form the internal electrode 202. The method may be described as an "outside-in substrate method" in which the first layer formed on the substrate is the inner electrode layer 202, then the electrolyte 206 layer, and then the outer electrode layer 204. The first and second electrodes may be anodes or cathodes. Sintering may include heating or EMR sintering.

In some embodiments, once the final electrode is formed, the substrate may then be removed. The substrate may be physically removed. The substrate may be dissolved and removed by a solvent. In some methods, the substrate may be composed of a low melting point material, such as a polymer, wherein the substrate may be melted or gasified and removed during any one of the thermal sintering steps. For example, the substrate may include a combustible material to burn off the substrate during one thermal sintering step.

In one embodiment, the first tube (internal or external) and electrolyte are sintered separately in an oven. In one embodiment, the first tube (inner orExternal) and electrolyte are co-sintered in an oven, which means that the first tube is coated with electrolyte material before sintering. A second tube (external or internal) is deposited on the electrolyte and then sintered using EMR, wherein the second tube comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel, and combinations thereof. FIGS. 4A-4D show using EMR various arrangements of source sintering tubes. The EMR source and the tube may be moved relative to each other, e.g., in an axial direction or in a helical trajectory, to ensure that the entire surface of the tube (internal or external) is sintered by exposing it sufficiently to the EMR source. In one embodiment, the EMR source is a xenon lamp, such as a circular xenon lamp, an elongated tubular xenon lamp, a point tubular xenon lamp.

Figures 4A-4D illustrate sintering methods and systems for producing tubular EC gas generators using EMR. Fig. 4A illustrates a portion of a method 400 of producing an EC gas generator using a single point EMR source, according to an embodiment of the disclosure. The EMR source (e.g., a xenon lamp) 402 and the tubular structure 404 can be moved relative to each other. As shown in fig. 4A, the single point EMR 402 can be rotated (e.g., in a spiral trace) about the tubular structure 404 in either direction as indicated by arrow 406. Alternatively, the tubular structure 404 may be rotated about the single point EMR 402. In another embodiment, the tubular structure 404 may rotate about its own axis 408 or move in an upward or downward direction 410 along its own long axis, or a combination thereof. The single point EMR source 402 can also be moved in an upward or downward direction 412.

Fig. 4B illustrates a portion of a method 420 of producing an EC gas generator using a ring light EMR source, according to an embodiment of the disclosure. As shown in fig. 4B, a circular ring lamp (e.g., a xenon lamp) 422 is shown as the EMR source, with the hollow circle in the center. The tubular structure 404 is centered on the annular lamp 422. In some embodiments, the tubular structure 404 may be moved up or down 410 or rotated 408 about its own axis while holding the ring light 422 in a fixed manner. In other embodiments, the tubular structure 404 may be held in a fixed manner while the ring light 422 may be moved along the length of the tubular structure 404. The ring light 422 may be moved in an upward or downward 424 manner, or in a rotation (426) of it about its own axis to ensure complete and thorough sintering. In other embodiments, both the tubular structure 402 and the ring lamp 422 may be capable of moving relative to each other to ensure thorough and complete sintering of the entire tubular structure 404. Fig. 4A-4B illustrate an embodiment in which the outer surface of the tubular structure 404 is sintered by EMR. These methods can be used to sinter anodes, cathodes electrolyte and other components of the tubular EC gas generator.

Fig. 4C-4D illustrate embodiments in which the inner surface of tubular structure 404 is sintered by EMR. Fig. 4C illustrates a portion of a method 440 of producing an EC gas generator using a single point EMR source, according to an embodiment of the disclosure. Figure 4C shows a single point EMR source disposed inside the tubular structure 404 (e.g., xenon lamp) 402. In a first embodiment, the tubular structure 404 may be held in a fixed manner while the single point EMR source may be moved in an upward or downward 412 manner. In a preferred embodiment, the single point EMR source 402 can irradiate all directions substantially equally. In another embodiment, the single point EMR source may be held in a fixed manner, while the tubular structure 404 may be moved in an upward or downward direction 410, or rotated 408 about its own axis. In another embodiment, the tubular structure 404 and the single point EMR source 402 are both moved relative to each other such that the entire inner surface of the tubular structure 404 is thoroughly and substantially sintered.

Fig. 4D shows a portion of a method 460 of producing an EC gas generator using a tubular EMR source, according to an embodiment of the disclosure. Fig. 3E4D shows a cylindrical lamp (e.g., a tubular xenon lamp) 462 as an EMR source disposed inside the tubular structure 404 to be sintered. In this case, the length of the lamp is such that the entire inner surface of the tubular structure 404 can be sintered without the tubular lamp 462 and the tubular structure 404 moving relative to each other. In one embodiment, the tubular lamp 462 may be held in a fixed manner, while the tubular structure 404 may be moved over the lamp 462. The tubular structure 404 may be moved in an upward or downward manner 464. For example, the unsintered tubular structure 404 may be moved over the tubular lamp 462 to the indicated position, held in that position until sufficient irradiation is performed and the tubular structure 404 is substantially sintered, and then moved in an upward or downward direction away from the tubular lamp 462 for the next production step, as indicated by arrow 464. In another embodiment, the unsintered tubular structure 404 may be held in a fixed position while the tubular lamp EMR source 462 is moved into the tubular structure 404. The tubular lamp 462 may be moved in an upward or downward manner, as indicated by arrow 464. The tubular structure 404 may be formed using any suitable method, such as the methods discussed herein. For the embodiment of fig. 4C-4D, coating and sintering occurs on the inner surface of tubular structure 404.

Many variations are possible for sintering as shown in fig. 4A-4D. For example, the outer tubular structure 204 may be formed and thermally sintered in a furnace to form an anode or cathode. The electrolyte material may then be coated onto the inner surface of the outer tubular structure 204 and then sintered in a furnace or using a single point EMR 402 or tubular lamp EMR 462 inside the tubular structure to form the electrolyte 206. Another electrode material may then be coated onto the inner surface of the electrolyte 206 and then sintered in a furnace or using the EMR sources 402, 462 to form the inner tubular structure 202, such as an anode or cathode. For example, for anodes containing copper, gold, or silver, the internal electrode is sintered using an EMR source. For example, for anodes containing Ni or NiO, the internal electrodes are sintered in a furnace or by an EMR source.

In some embodiments, sintering can be performed using a combination of an EMR source internal to the tubular electrodes 202, 204 or electrolyte 206 and an EMR source external to the tubular electrodes 202, 204 or electrolyte 206. For example, the tubular EMR source 462 and the ring-like EMR source 422 can be used in the same sintering device, sequentially or simultaneously.

Fig. 5A-5B illustrate another method of forming a first tube or tubes in an EC gas generator. Fig. 5A shows a first step in a cast molding process 500 for forming a tubular or multi-tubular EC gas generator, according to an embodiment of the present disclosure. In a first step, the support 504 is placed onto the substrate 502, wherein the height of the support 504 is preconfigured to ensure a desired thickness of the tubular electrode 506 on the bottom side. The substrate 502 and support 504 may be made of metal, glass, plastic, wood, or any suitable material known in the art. Electrode material 506 in the form of a dispersion or slurry is deposited on the substrate 502 between the supports 504. The term slurry will be used in the description, but the dispersion may also be used interchangeably. One or more shims (spacers) 508 are then placed on top of the slurry 506 and on the support 504. View 501 is a top or plan view further illustrating and showing examples of how substrate 502, support 504, electrode material 506, and spacer 508 may be arranged.

Fig. 5B shows steps 2-4 in a cast molding process 500 of forming a first tube or first multi-tube in an EC gas generator, according to an embodiment of the disclosure. In step 2, additional slurry 510 is deposited to cover the spacer 508 and the previously deposited slurry 506. A blade, such as a doctor blade, may be used to draw across the top of the additional slurry 510 to ensure a proper thickness of the tubular electrode on the top side. In a preferred embodiment, the slurry contains primarily organic solvents.

Step 3, shown in fig. 5B, includes immersing the substrate 502, support 504, spacer 508, first slurry 506, and second slurry 510 in deionized water to allow phase inversion of the slurries to occur. Phase inversion is a form of precipitation when a slurry comprising a low polarity organic solvent is placed in high polarity deionized water. Thus, the slurry components precipitate out because the components are not compatible with water.

Then, after phase inversion, the substrate 502 and the support 504 are removed from the slurry 506, 510 as a whole. The slurries 506, 510 are dried (e.g., in ambient air) to remove excess deionized water. The spacer 508 is then removed, e.g., pulled out from either end. The electrode materials 506, 510 are sintered to form a first tubular electrode 512 having a flow channel 514. The spacer 508 can have any regular or irregular shape, such as circular, oval, square, diamond, trapezoidal, rectangular, triangular, pentagonal, hexagonal, octagonal, or other various cross-sectional shapes or combinations thereof, as desired. If the spacer 508 has a rectangular cross-section, the plurality of connected tubular flow channels 514 will have the same rectangular cross-section as the flow channels 514 in the inner electrode 512 as shown in FIG. 3C. As can also be seen in fig. 3C-3D, the inner electrode 302 has a cross section with a length and a width, wherein the length is at least 2 times the width and the cross section is perpendicular to the axial direction of the tube. Similarly, the reactor has a cross section having a length and a width, wherein the length is at least 2 times the width and the cross section is perpendicular to the axial direction of the tube.

In one embodiment, the method shown in step 4 in fig. 5B further comprises coating the outer surface of the first tubular electrode 512 with an electrolyte material. The electrolyte material may then be sintered in an oven or by using electromagnetic radiation to form electrolyte 516. Step 4 also includes coating the electrolyte 516 with a second electrode material. The second electrode material may be sintered in an oven or using electromagnetic radiation to form the second outer tubular electrode 518. In one embodiment, the second electrode material comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel and combinations thereof; and sintered using EMR to form the second outer tubular electrode 518. In one embodiment, the method includes reducing the second outer tubular electrode 518 or reducing the first inner tubular electrode 512, or both.

In one embodiment, the coating step comprises dip coating, spray coating, ultrasonic spray coating, spin coating, brush coating, paste coating, or a combination thereof. In one embodiment, the electromagnetic radiation comprises UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, microwaves, or combinations thereof. In one embodiment, the electromagnetic radiation is provided by a xenon lamp. In one embodiment, the first tubular electrode 512 has a cross-section with a length and a width, wherein the length is at least 2 times the width and the cross-section is perpendicular to the axial direction of the tubular flow channel 514. In one embodiment, the EC gas generator does not include an interconnect.

EC gas generation operation of the device

Disclosed herein are methods comprising providing a device comprising a first electrode, a second electrode, and an electrolyte located between the electrodes, introducing a first stream into the first electrode, introducing a second stream into the second electrode, extracting hydrogen from the second electrode, wherein the first electrode and the second electrode comprise a metal phase that is free of platinum group metals when the device is in use. In one embodiment, the electrolyte is oxygen ion conductive. In one embodiment, the device is operated at a temperature of not less than 500 ℃, or not less than 600 ℃, or not less than 700 ℃. In one embodiment, the first stream comprises fuel and water or fuel and carbon dioxide. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the first stream is directed to the first electrode, or the second stream is directed to the second electrode, or both.

In one embodiment, the first stream comprises fuel with little to no water. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the second stream consists of water and hydrogen.

In one embodiment, the method includes providing a reformer upstream of the first electrode, wherein the first stream is passed through the reformer prior to introducing the first electrode, wherein the first electrode comprises Ni or NiO. In one embodiment, the reformer is a steam reformer or an autothermal reformer.

In one embodiment, the method is comprised in one of the following reactions: the extracted hydrogen is used in a fischer-tropsch (FT) reaction, a dry reforming reaction, a Sabatier (Sabatier) reaction catalyzed by nickel, a Bosch reaction, a reverse water gas shift reaction, an electrochemical reaction to generate electricity, the production of ammonia, the production of fertilizer, an electrochemical compressor or hydrogenation reaction for hydrogen storage, hydrogen vehicle fueling, or a combination thereof.

Disclosed herein are methods of producing hydrogen comprising providing an EC gas generator device, introducing a first stream comprising fuel into the device, introducing a second stream comprising water into the device, reducing water in the second stream to hydrogen, and extracting hydrogen from the device, wherein the first and second streams are not in contact with each other in the device. In one embodiment, the first stream does not contact hydrogen. In one embodiment, the first stream and the second stream are separated by a membrane in the device. In one embodiment, the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof. In one embodiment, the second stream comprises hydrogen. In one embodiment, the first stream comprises fuel and water or fuel and carbon dioxide. In one embodiment, the first stream comprises fuel with little to no water.

Hydrogen production system

Hydrogen production systems are further discussed herein, including a fuel source; a water source; a hydrogen generator; wherein the fuel source and the water source are in fluid communication with the generator, and wherein the fuel and the water are not in contact with each other in the generator. The system may not include an external heat source. In one embodiment, the fuel and water do not contact each other in the system. In one embodiment, a generator comprises a first electrode, a second electrode, and an electrolyte between the first and second electrodes; wherein the fuel source is in fluid communication with the first electrode and the water source is in fluid communication with the second electrode. In one embodiment, the fuel source provides heat to the hydrogen generator, and the hydrogen generator does not have other heat sources.

In one embodiment, the electrolyte comprises YSZ, CGO, LSGM, SSZ, SDC, ceria, lanthanum chromite, or a combination thereof, or wherein the electrolyte comprises doped or undoped ceria and optionally a material selected from the group consisting of YSZ, LSGM, SSZ and a combination thereof. In one embodiment of the present invention, in one embodiment, the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, lanthanum calcium chromite, or a combination thereof. The electrolyte may also include any of the materials listed for electrolyte 206 in the "tubular and multi-tubular EC gas generator" sections herein. In one embodiment, the electrolyte comprises doped ceria or wherein the electrolyte comprises lanthanum chromite or a conductive metal or a combination thereof and a material selected from the group consisting of doped ceria, YSZ, LSGM, SSZ, and a combination thereof. In one embodiment, the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, lanthanum calcium chromite, or a combination thereof. In one embodiment, the conductive metal comprises Ni, cu, ag, au or a combination thereof.

In one embodiment, the first and second electrodes comprise Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. In one embodiment, the first electrode comprises doped or undoped ceria and is selected from the group consisting of Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Stainless steel and combinations thereof; wherein the second electrode comprises Ni or NiO and a material selected from the group consisting of YSZ, CGO, samarium oxide doped ceria (SDC), scandia Stabilized Zirconia (SSZ), LSGM, and combinations thereof. The first and second electrodes may comprise any of the materials listed for the inner tubular structure 202 or the outer tubular structure 204 herein in the section "tubular and multi-tubular EC gas generator".

In one embodiment, the system comprises an oxidant source and a boiler (boiler), wherein the boiler is in fluid communication with the oxidant source, the water source and the generator. In one embodiment, the boiler is in thermal communication with the generator, a fuel input to the generator, an oxidant, water, or a combination thereof. In one embodiment, the boiler is configured to receive exhaust gas from a first electrode of the generator and feed steam into a second electrode of the generator. In one embodiment, the fuel is partially oxidized in the generator and further oxidized in the boiler. In one embodiment, the system includes a steam turbine positioned between and in fluid communication with the boiler and the generator.

In one embodiment, water is reduced in a generator to produce hydrogen. In one embodiment, the system includes a condenser configured to receive the exhaust gas from the second electrode of the generator and to recycle water back to the boiler and output hydrogen. In one embodiment, the condenser is in thermal communication with the fuel. In one embodiment, the system includes a desulfurization unit positioned between and in fluid communication with the fuel source and the generator. In one embodiment, the generator is configured to have a fuel inlet temperature of no greater than 1000 ℃, or no greater than 900 ℃, or 800 ℃ to 850 ℃. In one embodiment, the generator is configured to have a fuel outlet temperature of not less than 600 ℃.

Fig. 6A shows an example of a hydrogen production system 600 without an external heat source, according to an embodiment of the present disclosure. The system 600 includes a water source 602, an air/oxidant source 604, a fuel (e.g., methane) source 606, a hydrogen generator 608, and a boiler 610. The system 600 produces hydrogen 612 and exhaust. The hydrogen generator 608 includes an anode and a cathode separated by an electrolyte. The anode and cathode receive fuel and water, respectively, and the fuel and water do not contact each other in the generator 608. In many cases, the fuel and water do not contact each other throughout the system 600. The system itself fully satisfies the thermal load without any external heat source. For example, the boiler 610 heats the fuel input stream into the generator 608, the oxidant 604, and the water 602. The generator 608 in operation has a fuel inlet temperature of no greater than 1000 ℃, or no greater than 900 ℃, or 800 ℃ to 850 ℃, and has a fuel outlet temperature of no less than 600 ℃.

The fuel exits fuel source 606 as stream 600-1, passes through desulfurization unit 614 and becomes stream 600-2. Stream 600-2 enters condenser 616 and acts as a coolant to condenser 616 and exits as stream 600-3, which is a preheated fuel. Stream 600-3 enters heat exchanger (HX 2) 618 and is further heated to the appropriate temperature by exhaust stream 600-6 from boiler 610 and enters generator 608 as stream 600-4. Stream 600-4 is received through the anode in generator 608 and partially oxidized and then exits generator 608 as stream 600-5. Stream 600-5 is introduced into boiler 610 and is further oxidized by the oxidant in boiler 610, thereby generating heat. The flue gas exits from boiler 610 as stream 600-6 through heat exchanger HX2 618 to heat the fuel input into generator 608 and into stream 600-7. Stream 600-7 heats generator 608 to ensure proper operating temperature of generator 608 and becomes stream 600-19. Streams 600-19 pass through heat exchanger HX1 620 to heat the oxidant and exit as streams 600-20. Stream 600-20 passes through heat exchanger HX3 622 to heat water and exits as stream 600-21.

The water leaves the water source as stream 600-8, passes through the pump and becomes stream 600-9. Stream 600-9 is heated by stream 600-20 in heat exchanger HX3 622 and becomes stream 600-10. Stream 600-10 enters boiler 610 and is converted to steam by heat generated from the oxidation reaction in boiler 610 (stream 600-11). Stream 600-11 passes through turbine 624 and becomes stream 600-12. The turbine 624 is used to drive the pump. Stream 600-12 enters hydrogen generator 608 and is received by the cathode of generator 608. The water/steam is reduced to hydrogen at the cathode. The mixture of steam and hydrogen exits generator 608 as stream 600-13. Stream 600-13 enters condenser 616 and is cooled by unheated fuel (stream 600-2). The water is stripped from the mixture and recycled from the condenser as streams 600-18. Stream 600-18 is combined with stream 600-9 and reenters boiler 610 after passing through heat exchanger HX3 622. Hydrogen leaves condenser 616 as streams 600-14.

Air exits the oxidant source as streams 600-15 and passes through air cleaner 626 where particulates and/or oxides are removed and become streams 600-16. Stream 600-16 is heated in heat exchanger HX1 620 by stream 600-19 and becomes stream 600-17. Stream 600-17 enters boiler 610 and reacts with stream 600-5 to further oxidize the fuel and generate heat. The reaction product exits the boiler 610 as stream 600-6.

Fig. 6B shows an alternative hydrogen production system 650 without an external heat source, according to an embodiment of the present disclosure. Steam Generator (SG) 652 functions similarly to boiler 610 in system 600 in fig. 6A. Air enters the condenser as stream 650-1 and is used as a coolant in condenser 616. Air stream 650-2 is then heated in heat exchanger HX1 620 and mixed with the anode output stream before entering hydrogen generator 608 as stream 650-3. Fuel enters as stream 650-4 and is heated in heat exchanger HX2 618 by flue gas before entering hydrogen generator 608 as stream 650-5. The fuel is oxidized in the anode of the hydrogen generator 608 to an anode output stream and further oxidized by air to an exhaust 650-6. The flue gas provides thermal energy to heat exchangers (HX 1 620 and HX2 618) and SG 652 to generate steam from the water. The steam enters the hydrogen generator 608 and is reduced to hydrogen at the cathode. Cathode output stream 650-7 is introduced into condenser 616. The water from condenser 616 is recycled as stream 650-8 and hydrogen is extracted from condenser 616.

Fuel cell

Fuel cells are electrochemical devices that convert chemical energy from fuel into electricity through an electrochemical reaction. As described above, there are various types of fuel cells, for example, proton-exchange membrane fuel cells (PEMFC), solid Oxide Fuel Cells (SOFC). Fuel cells typically include an anode, a cathode, an electrolyte, an interconnect, an optional barrier layer, and/or an optional catalyst. Both the anode and the cathode are electrodes. In some cases, a list of materials for the electrodes, electrolyte, and interconnects in the fuel cell is applicable to the EC gas generator and EC compressor. These lists are examples only and are not limiting. Furthermore, the naming of the anode material and the cathode material is not limiting, as the function of the material during operation (e.g. whether it is oxidized or reduced) determines whether the material is to be used as an anode or a cathode.

Figures 7-8 illustrate various embodiments of fuel cells or components in a fuel cell stack. In these embodiments, the anode, cathode, electrolyte, and interconnect are rectangular parallelepiped or rectangular prisms.

Fig. 7 shows an assembly of a fuel cell according to an embodiment of the present disclosure. Layer 701 schematically shows an anode, layer 702 represents a cathode, layer 703 represents an electrolyte, layer 704 represents a barrier layer, layer 705 represents a catalyst and layer 706 represents an interconnect.

Fig. 8 schematically shows two fuel cells in a fuel cell stack according to an embodiment of the present disclosure. Two fuel cells are denoted as "fuel cell 1" and "fuel cell 2". Each fuel cell in fig. 8 includes an anode layer 801, a cathode layer 802, an electrolyte layer 803, a barrier layer 804, a catalyst layer 805, and an interconnect layer 806. As shown, two fuel cell repeating units or two fuel cells form a stack. As shown, on one side, the interconnect 806 is in contact with the largest surface of the cathode 802 of the fuel cell 2 (or fuel cell repeating unit), and on the opposite side, the interconnect 806 is in contact with the largest surface of the catalyst 805 (optional) or anode 801 of the bottom fuel cell 2 (or fuel cell repeating unit). By stacking on top of each other and sharing the interconnect located between them by direct contact with the interconnect rather than by wires, these repeating units or fuel cells are connected in parallel. This configuration shown in fig. 8 is in contrast to a segmented series (SIS) fuel cell.

Cathode electrode

In some embodiments, the cathode comprises a perovskite, such as LSC, LSCF, or LSM. In some embodiments, the cathode comprises one or more of lanthanum, cobalt, strontium, or manganites. In one embodiment, the cathode is porous. In some embodiments, the cathode includes one or more of YSZ, nitrogen boron doped graphene, la0.6sr0.4co0.2fe0.8o3, srco0.5sc0.5o3, bafe0.75ta0.25o3, bafe0.875re0.125o3, ba0.5la0.125zn0.375nio3, ba0.75sr0.25fe0.875ga0.125o3, bafe0.125co0.125, zr0.75o3. In some embodiments, the cathode comprises LSCo, LCo, LSF, LSCoF or a combination thereof. In some embodiments, the cathode comprises perovskite LaCoO3, laFeO3, laMnO3, (La, sr) MnO3, LSM-GDC, LSCF-GDC, LSC-GDC. The cathode containing LSCF is suitable for medium temperature fuel cell operation.

In some embodiments, 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.

Anode

In some embodiments, the anode comprises copper, nickel oxide-YSZ, niO-GDC, niO-SDC, aluminum doped zinc oxide, molybdenum oxide, lanthanum, strontium, chromite, ceria, and perovskite (e.g., LSCF [ La {1-x } Sr { x } Co {1-y } Fe { y } O ₃ ]Or LSM [ La {1-x } Sr { x } MnO ₃ ]Where x is typically in the range of 0.15-0.2 and y is in the range of 0.7 to 0.8). In some embodiments, the anode includes a SDC or BZTYYb coating or barrier layer to reduceLess coking and sulfur poisoning. In one embodiment, the anode is porous. In some embodiments, the anode comprises a combination of an electrolyte material and an electrochemically active material or a combination of an electrolyte material and a conductive material.

In a preferred embodiment, 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 stabilised ceria. In a preferred embodiment, the anode is formed by reduction of a material comprising nickel oxide and gadolinium stabilised ceria.

Electrolyte composition

In one embodiment, the electrolyte in the fuel cell comprises stabilized zirconia (e.g., YSZ-8, Y _0.16 Zr _0.84 O ₂ ). In one embodiment, the electrolyte comprises doped LaGaO3 (e.g., LSGM, la _0.9 Sr _0.1 Ga _0.8 Mg0.2O ₃ ). In one embodiment, the electrolyte comprises doped ceria (e.g., GDC, gd _0.2 Ce _0.8 O ₂ ). In one embodiment, the electrolyte comprises a stabilized bismuth oxide (e.g., BVCO, bi2V _0.9 Cu _0.1 O _5.35 ）。

In some embodiments, the electrolyte comprises zirconium oxide, yttria-stabilized zirconium oxide (also known as YSZ, YSZ8 (8 mol% YSZ)), ceria, gadolinium oxide, scandium oxide, magnesium oxide, or calcium oxide, or a combination thereof. In one embodiment, the electrolyte is sufficiently impermeable to prevent significant gas transport and to prevent significant electrical conduction (electrical conduction); and allows ionic conductivity. In some embodiments, the electrolyte comprises a doped oxide, such as cerium oxide, yttrium oxide, bismuth oxide, lead oxide, lanthanum oxide. In some embodiments, the electrolyte comprises a perovskite, such as LaCoFeO ₃ Or LaCoO ₃ Or Ce (Ce) _0.9 Gd _0.1 O ₂ (GDC) or Ce _0.9 Sm _0.1 O ₂ (SDC, samaria doped ceria) or scandia stabilized zirconia or a combination thereof.

In some embodiments, the electrolyte comprises a material selected from the group consisting of: zirconia, ceria and gallium oxide (gallia). In some embodiments, the material is stabilized with a stabilizing material selected from the group consisting of: scandium, samarium, gadolinium and yttrium. In one embodiment, the material comprises yttria-stabilized zirconia.

Interconnect element

In some embodiments, the interconnect comprises silver, gold, platinum, AISI441, ferritic stainless steel, lanthanum, chromium oxide, chromite, cobalt, cesium, cr ₂ O ₃ Or a combination thereof. In some embodiments, the anode comprises a metal alloy disposed at Cr ₂ O ₃ Or NiCo ₂ O ₄ Or MnCo ₂ O ₄ LaCrO on coating ₃ And (3) coating. In some embodiments, the interconnect surface is coated with cobalt and/or cesium. In some embodiments, the interconnect comprises a ceramic. In some embodiments, the interconnect comprises lanthanum chromite or doped lanthanum chromite. In one embodiment, the interconnect comprises a material that further comprises a metal, stainless steel, ferritic steel, crofer, lanthanum chromite, silver, a metal alloy, nickel oxide, ceramic, or lanthanum calcium chromite, or a combination thereof.

Catalyst

In various embodiments, the fuel cell includes a catalyst, such as platinum, palladium, scandium, chromium, cobalt, cesium, ceO ₂ Nickel, nickel oxide, zinc, copper, titanium dioxide, ruthenium, rhodium, moS ₂ Molybdenum, rhenium, vanadium, manganese, magnesium, or iron, or a combination thereof. In various embodiments, the catalyst facilitates a methane reforming reaction to produce hydrogen and carbon monoxide so that they can be oxidized in the fuel cell. Typically, the catalyst is part of an anode, in particular a nickel anode, which has inherent methane reforming properties. In one embodiment, the catalyst is present in an amount of 1% -5% or 0.1% to 10% by massAnd (3) the room(s). In one embodiment, a catalyst is used on the anode surface or in the anode. In various embodiments, these anode catalysts reduce detrimental coking reactions and carbon deposition. In various embodiments, a simple oxide form of the catalyst or perovskite may be used as the catalyst. For example, about 2% by mass of CeO ₂ The catalyst is used in methane driven fuel cells. In various embodiments, the catalyst may be immersed or coated on the anode. In various embodiments, the catalyst is prepared by an Additive Manufacturing Machine (AMM) and introduced into the fuel cell using the AMM.

The unique production methods discussed herein have described the assembly of ultra-thin fuel cells and fuel cell stacks. Typically, to achieve structural integrity, the fuel cell has at least one thick layer per repeating unit. This may be an anode (e.g., an anode-supported fuel cell) or an interconnect (e.g., an interconnect-supported fuel cell). As discussed above, the pressing or compression step is typically necessary to assemble the fuel cell assembly in a conventional production process to achieve hermeticity and/or proper electrical contact. As such, thick layers are necessary not only because conventional methods (such as cast molding) cannot produce ultra-thin layers, but also because the layers must be thick to withstand the extrusion or compression steps. The preferred production method of the present disclosure eliminates the need for extrusion or compression. The preferred production method of the present disclosure also enables the preparation of ultra-thin layers. The multiple layers in a fuel cell or fuel cell stack provide sufficient structural integrity for proper operation when they are prepared in accordance with the present disclosure.

Disclosed herein are fuel cells comprising anodes that are no greater than 1 mm, or 500 microns, or 300 microns, or 100 microns, or 50 microns, or no greater than 25 microns thick. The cathode has a thickness of no greater than 1 mm, or 500 microns, or 300 microns, or 100 microns, or 50 microns, or no greater than 25 microns. The electrolyte has a thickness of no greater than 1 mm, or 500 microns, or 300 microns, or 100 microns, or 50 microns, or 30 microns. In one embodiment, the fuel cell includes an interconnect having a thickness of not less than 50 microns. In some cases, the fuel cell comprises an anode no greater than 25 microns thick, a cathode no greater than 25 microns thick, and an electrolyte no greater than 10 microns or 5 microns thick. In one embodiment, the fuel cell includes an interconnect having a thickness of not less than 50 microns. In one embodiment, the thickness of the interconnect is in the range of 50 microns to 5 cm.

In a preferred embodiment, the fuel cell comprises an anode no greater than 100 microns thick, a cathode no greater than 100 microns thick, an electrolyte no greater than 20 microns thick, and an interconnect no greater than 30 microns thick. In a more preferred embodiment, the fuel cell comprises an anode no greater than 50 microns thick, a cathode no greater than 50 microns thick, an electrolyte no greater than 10 microns thick, and an interconnect no greater than 25 microns thick. In one embodiment, the thickness of the interconnect is in the range of 1 micron to 20 microns.

In a preferred embodiment, 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. In some cases, the barrier layer is an interconnect. In these cases, the reactants are injected directly into the anode and cathode.

In one embodiment, the cathode has a thickness of no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns. In one embodiment, the anode has a thickness of no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns. In one embodiment, 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 microns. In one embodiment, the interconnect is composed of a material comprising metal, stainless steel, silver, metal alloys, nickel oxide, ceramic, lanthanum chromite, doped lanthanum chromite, or lanthanum calcium chromite. In one embodiment, the total thickness of the fuel cell is not less than 1 micron.

Also discussed herein is a fuel cell stack comprising a plurality of fuel cells, wherein each fuel cell comprises an anode no greater than 25 microns thick, a cathode no greater than 25 microns thick, an electrolyte no greater than 10 microns thick, and an interconnect having a thickness in the range of 100 nm to 100 microns. In one embodiment, 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. In one embodiment, the barrier layer is an interconnect. For example, the interconnect is made of silver. For example, the thickness of the interconnect is in the range of 500 a nm a to 1000 a nm a. In one embodiment, the interconnect is composed of a material comprising metal, stainless steel, silver, a metal alloy, nickel oxide, ceramic, or lanthanum calcium chromite.

In one embodiment, the cathode has a thickness of no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns. In one embodiment, the anode has a thickness of no greater than 15 microns, or no greater than 10 microns, or no greater than 5 microns. In one embodiment, 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 microns. In one embodiment, the total thickness of each fuel cell is not less than 1 micron.

Further discussed herein are methods of making a fuel cell comprising (a) forming an anode no greater than 25 microns thick, (b) forming a cathode no greater than 25 microns thick, and (c) forming an electrolyte no greater than 10 microns thick. In one embodiment, steps (a) - (c) are performed using additive manufacturing. In various embodiments, the additive manufacturing uses one or more of extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination.

In one embodiment, the method includes assembling the anode, cathode, and electrolyte using additive manufacturing. In one embodiment, the method includes forming an interconnect and assembling the interconnect with an anode, a cathode, and an electrolyte.

In a preferred embodiment, the method comprises preparing at least one barrier layer. In a preferred embodiment, at least one barrier layer is used between the electrolyte and the cathode or between the electrolyte and the anode or both. In one embodiment, at least one barrier layer also functions as an interconnect.

In a preferred embodiment, the method includes heating the fuel cell to match shrinkage of the anode, cathode and electrolyte. In some embodiments, this heating is performed for no more than 30 minutes, preferably no more than 30 seconds, and most preferably no more than 30 milliseconds. When the fuel cell comprises a first composition and a second composition, wherein the first composition has a first shrinkage and the second composition has a second shrinkage, then the heating described in the present disclosure is preferably performed such that the difference between the first shrinkage and the second shrinkage is not greater than 75% of the first shrinkage.

In a preferred embodiment, electromagnetic radiation (EMR) is used for heating. In various embodiments, EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam. Preferably, the heating is performed in situ.

Also disclosed herein is a method of making a fuel cell stack comprising a plurality of fuel cells, the method comprising: (a) forming an anode no greater than 25 microns thick in each fuel cell, (b) forming a cathode no greater than 25 microns thick in each fuel cell, (c) forming an electrolyte no greater than 10 microns thick in each fuel cell, and (d) producing an interconnect in each fuel cell of 100 nm to 100 microns thick.

In one embodiment, steps (a) - (d) are performed using AM. In various embodiments, AM uses one or more of extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination methods.

In one embodiment, a method of making a fuel cell stack includes assembling an anode, a cathode, an electrolyte, and an interconnect using AM. In one embodiment, the method includes preparing at least one barrier layer in each fuel cell. In one embodiment, at least one barrier layer is used between the electrolyte and the cathode or between the electrolyte and the anode or both. In one embodiment, at least one barrier layer also functions as an interconnect.

In one embodiment, a method of making a fuel cell stack includes heating each fuel cell to match shrinkage of the anode, cathode, and electrolyte. In one embodiment, this heating is performed for no more than 30 minutes, or no more than 30 seconds, or no more than 30 milliseconds. In a preferred embodiment, the heating includes one or more electromagnetic radiations (EMR). In various embodiments, EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam. In one embodiment, the heating is performed in situ.

In one embodiment, the method includes heating the entire fuel cell stack to match shrinkage rates of the anode, cathode, and electrolyte. In some embodiments, this heating is performed for no more than 30 minutes, or no more than 30 seconds, or no more than 30 milliseconds.

A method of preparing an electrolyte is discussed herein that includes (a) formulating a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and particle size distributions, and a solvent; (b) forming an electrolyte comprising a colloidal suspension; and (c) heating at least a portion of the electrolyte; wherein the formulation of the colloidal suspension is preferably optimized by controlling the pH of the colloidal suspension, or the concentration of the binder in the colloidal suspension, or the composition of the binder in the colloidal suspension, or the diameter range of the particles, or the largest diameter of the particles, or the median particle diameter of the particles, or the particle size distribution of the particles, or the boiling point of the solvent, or the surface tension of the solvent, or the composition of the solvent, or the thickness of the smallest dimension of the electrolyte, or the composition of the particles, or a combination thereof.

Methods of making a fuel cell are discussed herein that include (a) obtaining a cathode and an anode; (b) modifying the cathode surface and the anode surface; (c) Preparing a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and particle size distributions, and a solvent; (d) Forming an electrolyte comprising a 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 the pH of the colloidal suspension, or the concentration of the binder in the colloidal suspension, or the composition of the binder in the colloidal suspension, or the diameter range of the particles, or the largest diameter of the particles, or the median particle diameter of the particles, or the particle size distribution of the particles, or the boiling point of the solvent, or the surface tension of the solvent, or the composition of the solvent, or the thickness of the smallest dimension of the electrolyte, or the composition of the particles, or a combination thereof. In various embodiments, the anode and cathode are obtained by any suitable method. In one embodiment, the modified anode surface and the modified cathode surface have a maximum height profile roughness (maximum height profile roughness) that is less than the average diameter of the particles in the colloidal suspension. Maximum height profile roughness 900 refers to the maximum distance between any grooves 902 and adjacent peaks 904 of the anode or cathode surface as shown in fig. 9. In various embodiments, the anode surface and the cathode surface are modified by any suitable method.

Further disclosed herein are methods of making a fuel cell comprising (a) obtaining a cathode and an anode; (b) Preparing a colloidal suspension, wherein the colloidal suspension comprises an additive, particles having a range of diameters and particle size distributions, and a solvent; (c) Forming an electrolyte comprising a colloidal suspension between an anode and a cathode; and (d) heating at least a portion of the electrolyte; wherein formulating the colloidal suspension comprises controlling the pH of the colloidal suspension, or the concentration of the binder in the colloidal suspension, or the composition of the binder in the colloidal suspension, or the diameter range of the particles, or the largest diameter of the particles, or the median particle diameter of the particles, or the particle size distribution of the particles, or the boiling point of the solvent, or the surface tension of the solvent, or the composition of the solvent, or the thickness of the smallest dimension of the electrolyte, or the composition of the particles, or a combination thereof. In various embodiments, the anode and cathode are obtained by any suitable method. In one embodiment, 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.

In a preferred embodiment, the solvent comprises water. In a preferred embodiment, the solvent comprises an organic component. The solvent may include ethanol, butanol, alcohol, terpineol, diethyl ether, 1, 2-dimethoxyethane (DME (ethylene glycol dimethyl ether), 1-propanol (n-propanol, n-propyl alcohol), or butanol, or a combination thereof.

In some embodiments, the electrolyte is formed adjacent to the first substrate or between the first substrate and the second substrate. In some embodiments, the first substrate has a maximum height profile roughness that is less than the average diameter of the particles. In some embodiments, the particles have a bulk density of greater than 40%, or greater than 50%, or greater than 60%. In one embodiment, the particles have a bulk density that approximates a Random Close Packing (RCP) density.

Random close packing density (RCP) is an empirical parameter used to characterize the maximum volume fraction of solid objects obtained at random packing. The container is randomly filled with objects and then shaken or tapped until the objects are no longer compacted, at which point the build-up condition is RCP. The fraction of the pack is the volume occupied by a number of particles in a given volume. The number of stacked portions determines the stacking density. For example, when a solid container is filled with particles, shaking the container will reduce the volume occupied by the object, thus allowing more particles to be added to the container. Shaking increases the density of the stacked objects. When shaking no longer increases the packing density, a limit is reached and if this limit is reached and there is no significant packing into the tetragonal lattice, this is an empirical random close packing density.

In some embodiments, the median particle size is between 50 nm and 1000 nm, or between 100 nm and 500 nm, or about 200 nm. In some embodiments, 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 the median particle diameter of the first substrate and no less than 1/10 of it. In some embodiments, the first substrate comprises a bimodal particle size distribution having a first mode and a second mode, wherein each peak has a median particle size. In some embodiments, the median particle size of 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 alter the behavior of the first substrate during heating. In some embodiments, the first substrate has a shrinkage that varies with heating temperature. In some embodiments, the particles in the colloidal suspension may have a maximum particle size and a minimum particle size, wherein the maximum particle size is less than 2 times, or less than 3 times, or less than 5 times, or less than 10 times the minimum particle size. In some embodiments, the minimum size of the electrolyte is less than 10 microns, or less than 2 microns, or less than 1 micron, or less than 500 nm.

In some embodiments, the electrolyte has a gas permeability of no greater than 1 millidarcy, preferably no greater than 100 micro darcy, and most preferably no greater than 1 micro darcy. Preferably, the electrolyte does not have a minimum size of cracks penetrating through the electrolyte. In some embodiments, the boiling point of the solvent is no less than 200 ℃, or no less than 100 ℃, or no less than 75 ℃. In some embodiments, the solvent has a boiling point of no greater than 125 ℃, or no greater than 100 ℃, or no greater than 85 ℃, or no greater than 70 ℃. In some embodiments, the pH of the colloidal suspension is not less than 7, or not less than 9, or not less than 10.

In some embodiments, the additive comprises polyethylene glycol (PEG), ethylcellulose, polyvinylpyrrolidone (PVP), polyvinyl butyral (PVB), butyl Benzyl Phthalate (BBP), polyalkylene glycol (PAG), or a combination thereof. In one embodiment, 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.

In one embodiment, the colloidal suspension is ground. In one embodiment, a rotating mill is used to grind the colloidal suspension, wherein the rotating mill is operated at not less than 20 rpm, or not less than 50 rpm, or not less than 100 rpm, or not less than 150 rpm. In one embodiment, a colloidal suspension is milled using zirconia milling balls or tungsten carbide balls, wherein the colloidal suspension is milled for not less than 2 hours, or not less than 4 hours, or not less than 1 day, or not less than 10 days.

In some embodiments, the concentration of particles 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 concentration of particles in the colloidal suspension is not less than 2 wt%. In some embodiments, the concentration of particles 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 one embodiment, the concentration of particles in the colloidal suspension is not less than 0.1 vol%.

In a preferred embodiment, the electrolyte is formed using an Additive Manufacturing Machine (AMM). In a preferred embodiment, the first substrate is formed using AMM. In a preferred embodiment, the heating includes the use of electromagnetic radiation (EMR), wherein the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, or laser light. In a preferred embodiment, the first substrate and the electrolyte are heated to cause co-sintering. In a preferred embodiment, the first substrate, the second substrate and the electrolyte are heated to cause co-sintering. In one embodiment, the EMR is controlled to preferentially sinter the first substrate relative to the electrolyte.

In one embodiment, the electrolyte is compressed after heating. In one embodiment, the first and second substrates exert pressure on the electrolyte after heating. In one embodiment, the first and second substrates to which pressure is applied are the anode and cathode of a fuel cell. In some embodiments, the minimum size of the electrolyte is between 500 nm and 5 microns or between 1 and 2 microns.

The detailed discussion described herein uses the production of Solid Oxide Fuel Cells (SOFCs) as an illustrative example. As will be appreciated by those skilled in the art, the methods and production methods described herein are applicable to all fuel cell types. As such, production of all fuel cell types is within the scope of the present disclosure.

Reactor box (reactor cartridge)

In various embodiments, an Electrochemical (EC) reactor is formed in the form of a cartridge. The discussion herein uses a fuel cell or fuel cell stack as an example. The cartridge design is applicable to other electrochemical reactors such as EC gas generators, EC compressors, flow batteries (flow batteries). In various embodiments, the fuel cell stack is configured in the form of a cartridge, such as an easily removable flange Fuel Cell Cartridge (FCC) design. Fig. 9A shows a perspective view of a Fuel Cell Cartridge (FCC) 900, in accordance with an embodiment of the disclosure. The FCC 900 includes a rectangular shape as shown in fig. 9A. Other form factors are possible, such as square-like, cylindrical-like, hexagonal-like, or combinations thereof. The form factor may depend on the application in which the FCC is used, such as in industrial, home, automotive, or other applications. The FCC 900 also includes holes 902 for bolts that fasten the FCC in the system or in series with other FCC's or both. The housing of the FCC unit 900 may be comprised of aluminum, steel, plastic, ceramic, or a combination thereof. The FCC 900 includes a top interconnect 904.

Fig. 9B shows a perspective view of a cross section of a Fuel Cell Cartridge (FCC) 900, in accordance with an embodiment of the disclosure. The FCC 900 includes bolt holes 902, cathode layer 906, barrier layer 908, anode layer 910, gas channels 912 in the electrodes (anode and cathode), electrolyte layer 914, air heat exchanger 916, fuel heat exchanger 918, and top interconnect 904. The combined air heat exchanger 916 and fuel heat exchanger 918 form an integrated multi-fluid heat exchanger. In some embodiments, there is no barrier layer between the cathode 906 and the electrolyte 914. The FCC 900 includes a second interconnect 920, such as between the anode layer 910 and the fuel heat exchanger 918. The FCC 900 also includes openings 922, 924 for fuel passages.

Fig. 9C shows a cross-sectional view of a Fuel Cell Cartridge (FCC) in accordance with an embodiment of the disclosure. The FCC 900 in fig. 9C includes an electrical bolt insulation (electrical bolt isolation) 926, an anode 910, a seal 928 isolating the anode 910 from the air flow, a cathode 906, and a seal 930 isolating the cathode 906 from the fuel flow. The bolts may also be electrically insulated by sealing. In various embodiments, the seal may be a Dual Function Seal (DFS) comprising YSZ (yttria stabilized zirconia) or 3YSZ (ZrO ₂ Y in 3 mol% ₂ O ₃ ) And 8YSZ (ZrO ₂ Y of 8 mol% ₂ O ₃ ) Is a mixture of (a) and (b). In some embodiments, the DFS is impermeable to non-ionic species and is electrically insulating. In some embodiments, the mass ratio of 3YSZ/8YSZ is in the range of 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.

Fig. 9D shows top and bottom views of a Fuel Cell Cartridge (FCC) according to an embodiment of the disclosure. The FCC 900 includes bolt holes 902, air inlets 932, air outlets 934, fuel inlets 922, fuel outlets 924, bottom 936 and top interconnects 904 of the FCC 900. FIG. 9D also shows top and bottom views of an embodiment of the FCC 900, where the length of the oxidant side of the FCC 900 is shown as L _o The length of the fuel side of the FCC 900 is shown as L _f The width of the oxidant (air inlet 932) inlet is shown as W _o And the width of the fuel inlet 922 is shown as W _f . In fig. 9D, two fluid outlets (air outlet 934 and fuel outlet 924) are shown. In some embodiments, the anode exhaust gas and the cathode exhaust gas may be mixed and extracted through one fluid outlet. In some cases, the bottom 936 is an interconnect and 932, 934, 922, 924 are openings of the flow channels, e.g., in a direction perpendicular to the lateral direction.

Disclosed herein is a Fuel Cell Cartridge (FCC) 900 comprising an anode 910, a cathode 906, an electrolyte 914, at least one interconnect, a fuel inlet on a fuel side of the FCC 900, an oxidant inlet on an oxidant side of the FCC, at least one fluid outlet, wherein the fuel inlet has W _f Has a width of L on the fuel side of FCC _f Is provided with W _o Has a width L on the oxidant side of FCC _o Wherein W is _f /L _f Within the following ranges: 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, and W _o /L _o Within the following ranges: 0.1 to 1.0, alternatively 0.1 to 0.9, alternatively 0.2 to 0.9, alternatively 0.5 to 1.0.

In some embodiments, the air and fuel inlets and outlets are on a surface of the FCC 900, wherein the FCC 900 does not include protruding flow channels (protruding fluid passage, protruding flow channels) on the surface. In some embodiments, the surface is smooth with a maximum rise change of no more than 1 mm, or no more than 100 microns, or no more than 10 microns.

In some embodiments, the FCC 900 includes a barrier layer between the electrolyte and the cathode or between the electrolyte and the anode or both. In one embodiment, the FCC includes a Dual Function Seal (DFS) that is impermeable to non-ionic species and electrically insulating. In some embodiments, the DFS comprises YSZ (yttria stabilized zirconia) or 3YSZ (ZrO ₂ Y in 3 mol% ₂ O ₃ ) And 8YSZ (ZrO ₂ Y of 8 mol% ₂ O ₃ ) Is a mixture of (a) and (b).

In some embodiments, the interconnect does not contain a fluid dispersion element, and the anode and cathode contain a fluid dispersion assembly. In some embodiments, the interconnect does not contain a fluid dispersion element, and the anode and cathode contain fluid channels.

In some embodiments, a Fuel Cell Cartridge (FCC) 900 includes an anode, a cathode, an electrolyte, an interconnect, a fuel inlet, an oxidant inlet, at least one fluid outlet, wherein the inlet and outlet are located on one surface of the FCC, and the FCC does not include protruding flow channels located on the surface. In some embodiments, the surface may be smooth with a maximum rise change of no more than 1 mm, or no more than 100 microns, or no more than 10 microns.

In some embodiments, the FCC 900 includes DFS that is impermeable to non-ionic species and electrically insulating. In one embodiment, the interconnect does not contain a fluid dispersion element, and the anode and cathode contain a fluid dispersion assembly. In one embodiment, the interconnect does not contain a fluid dispersion element, and the anode and cathode contain fluid channels.

In one embodiment, the FCC 900 is removably secured to a mating surface (mating surface) and is not welded or soldered to the mating surface. In one embodiment, the FCC is bolted or extruded to the mating surface. The mating surface includes a mating fuel inlet, a mating oxidant inlet, and at least one mating fluid outlet.

Also disclosed herein is an assembly comprising a Fuel Cell Cartridge (FCC) and a mating surface, wherein the FCC comprises an anode, a cathode, an electrolyte, an interconnect, a fuel inlet to a fuel side of the FCC, an oxidant inlet to an oxidant side of the FCC, at least one fluid outlet, wherein the fuel inlet has a W _f Has a width of L on the fuel side of FCC _f Is provided with W _o Has a width L on the oxidant side of FCC _o Wherein W is _f /L _f Within the following ranges: 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, and W _o /L _o Within the following ranges: 0.1 to 1.0, or 0.1 to 0.9, or 0.2 to 0.9, or 0.5 to 1.0, wherein the FCC is removably secured to the mating surface.

In some embodiments, the inlet and outlet are on one surface of the FCC, and wherein the FCC does not include protruding flow channels on said surface. The surface may be smooth with a maximum rise variation of no more than 1 mm, or no more than 100 microns, or no more than 10 microns.

In one embodiment, the interconnect does not include a fluid dispersion element, and the anode and cathode include a fluid dispersion assembly. In one embodiment, the interconnect does not include a fluid dispersion element, and the anode and cathode include fluid channels.

Methods are discussed herein that include extruding or bolting a Fuel Cell Cartridge (FCC) and a mating surface together. The method does not include welding or soldering together the FCC and mating surfaces, wherein the FCC includes an anode, a cathode, an electrolyte, an interconnect, a fuel inlet on a fuel side of the FCC, an oxidant inlet on an oxidant side of the FCC, at least one fluid outlet, wherein the fuel inlet has a width W _f The FCC fuel side has a length L _f The oxidant inlet has a width W _o ，FThe oxidant side of CC has length L _o Wherein W is _f /L _f 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 1.0, and W _o /L _o 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 1.0, wherein the FCC and mating surfaces are removable.

In one embodiment, the inlet and outlet are on one surface of the FCC, wherein the FCC does not include protruding flow channels on the surface. The surface is smooth with a maximum rise variation of no more than 1 mm, or no more than 100 microns, or no more than 10 microns. In one embodiment, the interconnect does not include a fluid dispersion element, and the anode and cathode include a fluid dispersion assembly. In one embodiment, the interconnect does not include a fluid dispersion element, and the anode and cathode include fluid channels.

Disclosed herein is a Fuel Cell Cartridge (FCC) comprising a fuel cell and a fuel cell housing, wherein the fuel cell comprises an anode, a cathode, and an electrolyte, wherein at least a portion of the fuel cell housing is made of the same material as the electrolyte. In one embodiment, the electrolyte is in contact with a portion of a fuel cell housing made of the same material. In one embodiment, the electrolyte and a portion of the fuel cell housing are made of DFS, wherein DFS comprises 3YSZ (ZrO ₂ Y in 3 mol% ₂ O ₃ ) And 8YSZ (ZrO ₂ Y of 8 mol% ₂ O ₃ ) Wherein the mass ratio of 3YSZ/8YSZ is in the following range: 100/0 to 0/100 or 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, 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.

In one embodiment, the fuel cell housing contains a fuel inlet and fuel channel for the anode, an oxidant inlet and oxidant channel for the cathode, and at least one fluid outlet. In one embodiment, the inlet and the at least one outlet are located on one surface of the FCC, wherein the FCC does not include protruding flow channels located on the surface. In one embodiment, the fuel cell housing is in contact with at least a portion of the anode.

In one embodiment, the FCC includes a barrier layer between the electrolyte and the cathode and between the fuel cell housing and the cathode. In one embodiment, the FCC includes an interconnect, wherein the interconnect does not include a fluid dispersion element, and the anode and cathode include a fluid dispersion assembly. In one embodiment, the FCC includes an interconnect, wherein the interconnect does not include a fluid dispersion element, and the anode and cathode include fluid channels.

In one embodiment, the FCC is removably secured to the mating surface and is not welded or soldered to the mating surface. In one embodiment, the mating surface includes a mating fuel inlet, a mating oxidant inlet, and at least one mating fluid outlet.

Also discussed herein are compositions comprising 3YSZ (ZrO ₂ Y in 3 mol% ₂ O ₃ ) And 8YSZ (ZrO ₂ Y of 8 mol% ₂ O ₃ ) Wherein the mass ratio of 3YSZ/8YSZ is in the range of 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, 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. In one embodiment, the DFS is used as an electrolyte in a fuel cell or as a part of a fuel cell housing or both.

Also disclosed herein are methods comprising providing a DFS in a fuel cell system, wherein the DFS comprises 3YSZ (ZrO ₂ Y in 3 mol% ₂ O ₃ ) And 8YSZ (ZrO ₂ Y of 8 mol% ₂ O ₃ ) Wherein the mass ratio of 3YSZ/8YSZ is in the following range: 100/0 to 0/100 or 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, 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.

In one embodiment, DFS is used as part of the electrolyte or fuel cell housing or both in a fuel cell system. A portion of the fuel cell housing may be the entire fuel cell housing. A portion of the fuel cell housing is a coating on the fuel cell housing. An electrolyte is in contact with a portion of the fuel cell housing.

Disclosed herein is a fuel cell system comprising an anode having 6 surfaces, a cathode having 6 surfaces, an electrolyte, and an anode surround in contact with at least 3 surfaces of the anode, wherein the electrolyte is part of the anode surround, and the anode surround is made of the same material as the electrolyte. In one embodiment, the same material is a material comprising 3YSZ (ZrO ₂ Y in 3 mol% ₂ O ₃ ) And 8YSZ (ZrO ₂ Y of 8 mol% ₂ O ₃ ) Wherein the mass ratio of 3YSZ/8YSZ is in the following range: 100/0 to 0/100 or 10/90 to 90/10, and wherein the DFS is impermeable to non-ionic species and electrically insulating. In one embodiment, 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. In one embodiment, the anode enclosure is in contact with 5 surfaces of the anode.

In one embodiment, a fuel cell system comprises a barrier layer between a cathode and a cathode surround (cathode surround), wherein the barrier layer is in contact with at least 3 surfaces of the cathode, wherein an electrolyte is part of the cathode surround, and the cathode surround is made of the same material as the electrolyte.

In one embodiment, a fuel cell system includes fuel channels and oxidant channels in an anode enclosure and a cathode enclosure. In one embodiment, the fuel cell system comprises an interconnect, wherein the interconnect does not comprise a fluid dispersion element, and the anode and cathode comprise a fluid dispersion assembly. In one embodiment, the fuel cell system comprises an interconnect, wherein the interconnect does not comprise a fluid dispersion element, and the anode and cathode comprise fluid channels.

Tubular design

In many cases, the electrochemical reactor as discussed in this disclosure is tubular. The discussion in this section takes a Tubular Fuel Cell (TFC) as an example of a tubular electrochemical reactor. The tubular design is applicable to other types of electrochemical reactors, such as EC gas generators, EC compressors or flow cells. Disclosed herein is a Tubular Fuel Cell (TFC) comprising an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect. In some embodiments of TFC, the electrolyte is considered a membrane. The cross-section of the cathode is a rounded non-circular shape (rounded non-circular shape) without sharp corners, wherein the cross-section is perpendicular to the longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but not with the anode, and the interconnect has a contact surface configured to contact the anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, the TFC comprises a barrier layer between the cathode and the electrolyte or between the anode and the electrolyte or both. In one embodiment, the rounded non-circular shape includes a rounded rectangle, rounded square, rounded hexagon, rounded trapezoid, rounded parallelogram, rounded pentagon, rounded triangle, rounded octagon, oval, ellipsoid, or rounded irregular shape, or a combination thereof.

In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 1, or no greater than 0.75, or no greater than 0.5. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 0.3, or no greater than 0.1, or no greater than 0.05.

In one embodiment, the thickness of the cathode is in the following range: about 10 microns to about 1,000 microns; or about 50 to about 150 microns; or about 90 to about 110 microns; or about 100 microns. In one embodiment, the thickness of the anode is in the following range: about 1 micron to about 50 microns; or about 5 microns to about 25 microns; or about 8 microns to about 12 microns; or about 10 microns. In one embodiment, the electrolyte has a thickness in the following range: about 100 nm to about 10 microns; or about 500 nm to about 5 microns; or about 800 nm to about 2 microns; or about 1 micron. In one embodiment, the thickness of the barrier layer is in the following range: about 100 nm to about 10 microns; or about 500 nm to about 5 microns; or about 800 nm to about 2 microns; or about 1 micron. In one embodiment, the thickness of the interconnect is in the following range: about 10 microns to about 1000 microns; or about 50 microns to about 500 microns; or about 80 microns to about 200 microns; or about 100 microns.

In one embodiment, the TFC has a length L and the cross section has a characteristic length W, wherein the ratio of L/W is not less than 1. In one embodiment, the ratio of L/W is not less than 2, or not less than 10, or not less than 100.

In one embodiment, the TFC includes a support in the cathode. In one embodiment, the support is in contact with the cathode. In one embodiment, the support is an integral part of the cathode. In one embodiment, the support and the cathode are made of the same material. In one embodiment, the support and the cathode are made of different materials. In one embodiment, the electrolyte is impermeable to the fluid. In one embodiment, the cathode and anode are porous.

Also discussed herein is a fuel cell stack comprising a plurality of Tubular Fuel Cells (TFCs), wherein each of the TFCs comprises an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the cathode is a rounded non-circular shape having no sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but is not in contact with the anode, and the interconnect has a contact surface configured to contact an anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact an interconnect of another adjacent TFC.

In one embodiment, each of the TFCs comprises a barrier layer located between the cathode and the electrolyte or between the anode and the electrolyte or both. In one embodiment, the rounded non-circular shape comprises a rounded rectangle, rounded square, rounded hexagon, rounded trapezoid, rounded parallelogram, rounded pentagon, rounded triangle, rounded octagon, oval, ellipsoid, or rounded irregular shape.

In one embodiment, each of the TFCs has a length L and the cross section has a characteristic length W, wherein the ratio of L/W is not less than 1, or not less than 2, or not less than 10, or not less than 100.

In one embodiment, each of the TFCs comprises a support located in the cathode. In one embodiment, the support is in contact with the cathode. In one embodiment, the support is an integral part of the cathode. In one embodiment, the support and the cathode are made of the same material.

Disclosed herein is a Tubular Fuel Cell (TFC) comprising an inner anode, an outer cathode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein a cross-section of the anode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to a longitudinal axis of the TFC, wherein the interconnect is in contact with the anode but not with the cathode, and the interconnect has a contact surface configured to contact a cathode of an adjacent TFC, wherein the cathode has a contact surface and a non-contact surface configured to contact an interconnect of another adjacent TFC.

In one embodiment, the rounded non-circular shape includes a rounded rectangle, a rounded square, a rounded hexagon, a rounded trapezoid, a rounded parallelogram, a rounded pentagon, a rounded triangle, a rounded octagon, an oval, an ellipsoid, a rounded irregular shape, or a combination thereof. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the cathode is no greater than 1, or no greater than 0.75, or no greater than 0.5, no greater than 0.3, or no greater than 0.1, or no greater than 0.05. In one embodiment, the TFC comprises a barrier layer between the cathode and the electrolyte or between the anode and the electrolyte or both.

Fig. 10A-10C show different aspect ratios (aspect ratios) of fuel cells and how they may be connected in a multi-Tubular Fuel Cell (TFC) unit that contains two or more TFCs. TFC includes rounded edges. Fig. 10A shows a cross-sectional view of TFC 1000 in accordance with an embodiment of the present disclosure. TFC 1000 includes an inner cathode layer 1002, a barrier layer 1004, an electrolyte layer 1006, an outer anode layer 1008, interconnects 1010, and runners 1012. In some cases, a barrier layer 1004 is disposed between the anode 1008 and the electrolyte 1006. In some cases, two barrier layers are placed (1) between cathode 1002 and electrolyte 1006 and (2) between anode 1008 and electrolyte 1006. Interconnect 1010 is in contact with cathode 1002 but not anode 1008. The top surface of the interconnect 1010 is configured to contact the anode 1008 of an adjacent TFC. The anode 1008 has a contact surface on the bottom configured to contact the interconnect 1010 of another adjacent TFC. The anode 1008 has non-contact surfaces on both sides in the configuration shown in fig. 10A-10C. In this example in fig. 10A, TFC 1000 has a rounded rectangular shape that is connected by an interconnect 1010 located on the short end of the rectangular shape.

Fig. 10B shows a cross-sectional view of TFC 1020, in accordance with an embodiment of the present disclosure. TFC 1020 is similar in construction to TFC 1000, but is connected by an interconnect 1010 on the long side of the rectangular shape.

Fig. 10C shows a cross-sectional view of TFC 1040 in accordance with an embodiment of the disclosure. TFC 1040 in fig. 10C is similar in structure to the TFC in fig. 10A-10B, but includes a rounded square-like shape with the length of each side being substantially the same. TFC 1040 is further connected by interconnect 1010.

In alternative embodiments, the anode 1008 may be configured internal and the cathode 1002 may be external. In some cases, a barrier layer may be disposed between the cathode and the electrolyte. In some cases, two barrier layers are placed (1) between the cathode and the electrolyte and (2) between the anode and the electrolyte. All other configurations and features as discussed above are also applicable in this embodiment.

In some embodiments, as shown in fig. 11A-11C, the TFC may also include one or more supports located in the cathode layer. Fig. 11A shows a cross-sectional view of a TFC 1100 that includes a support according to an embodiment of the present disclosure. TFC 1100 includes a cathode 1002, a barrier layer 1004, an electrolyte 1006, an anode layer 1008, an interconnect 1010, and at least one runner 1012. How to arrange the shape and design of TFC 1100 is similar to the TFC in fig. 10A. TFC 1100 also includes one or more supports. The support may be in any suitable shape, number, size and material. In some cases, the support 1102 is made of the same material as the internal electrode layers, such as the cathode layer 1002. In some cases, the support 1104 is made of a material that is different from the material of the internal electrode layers, such as the cathode 1002. For example, inert materials with respect to fuel cells. In some cases, the support may be made of more than one material. In one embodiment, one or more supports 1102, 1104 are in contact with the cathode 1002. In one embodiment, one or more of the supports 1102, 1104 are an integral part of the cathode. In one embodiment, one or more supports 1102, 1104 are made as an integral part of the cathode.

Fig. 11B shows a cross-sectional view of TFC 1120 including a support according to an embodiment of the present disclosure. How to arrange the TFC 1120 is similar in shape and design to the TFC in fig. 10B. TFC 1120 also includes one or more supports. The support 1102 may be a support having a linear shape of the same material as the internal electrode, such as the cathode 1002. The support 1104 may be a linear-shaped support 1104 that is not composed of the same material. The support 1106 may be an oval or circular-like shaped support composed of the same material as the internal electrode, such as the cathode 1002. The support 1108 may be an oval or circular-like shaped support that is not composed of the same material as the internal electrode, such as cathode 1002. As shown in fig. 11B, the TFC may include linear shape supports 1102, 1104 and circular shape supports 1106, 1108.

Fig. 11C shows a cross-sectional view of TFC 1140 including a support according to an embodiment of the disclosure. How to arrange the TFC 1140 is similar in shape and design to the TFC in fig. 10C. TFC 1140 also includes one or more supports. In this embodiment, all of the supports 1106, 1108 may be circular-like or oval-like in shape, although linear-shaped supports 1102, 1104 may also be used.

In some embodiments, the internal electrode may be an anode layer 1008 in TFC 1100, 1120, 1140. The supports 1102, 1104, 1106, 1108 may be composed of the same material as the inner anode layer or may not be composed of the anode layer 1008 or a combination thereof.

Methods are discussed herein that include placing a fluid mixture between two Tubular Fuel Cells (TFCs), wherein the two TFCs have a gap with a minimum distance of no more than 1 mm; heating the fluid mixture, thereby connecting the two TFCs; wherein the fluid mixture has a viscosity of no greater than 1000 centipoise. In one embodiment, the viscosity of the fluid mixture is no greater than 500 centipoise, or no greater than 300 centipoise, or no greater than 200 centipoise, or no greater than 100 centipoise, or no greater than 50 centipoise. In one embodiment, the minimum distance of the gap is no greater than 500 microns, or no greater than 300 microns, or no greater than 200 microns, or no greater than 100 microns, or no greater than 50 microns.

In one embodiment, disposing the fluid mixture includes aerosol jetting, material jetting, inkjet printing, or a combination thereof. In one embodiment, the fluid mixture comprises a fluid and a solid, and wherein heating the fluid mixture causes the fluid to escape and the solid to remain. In one embodiment, heating the fluid mixture causes it to cure. In one embodiment, heating includes the use of electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, microwaves, or combinations thereof. In one embodiment, the heating comprises oven heating, furnace heating, kiln heating, plasma heating, hot surface heating, or a combination thereof. In one embodiment, heating is accomplished by conduction, convection, radiation, or a combination thereof. In one embodiment, the heating results in sintering, co-sintering, annealing, densification, curing, evaporating, drying, or a combination thereof.

In one embodiment, the fluid mixture comprises gold, silver, platinum, nickel, iron, steel, stainless steel, chromium, cobalt, carbon, or inconel (inconel). In one embodiment, the fluid mixture comprises a material for an electrode in a fuel cell or a material for an interconnect in a fuel cell, or both.

In one embodiment, each TFC comprises an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein the cross-section of the cathode is a rounded non-circular shape with no sharp corners, wherein the cross-section is perpendicular to the longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but not with the anode, and the interconnect has a contact surface configured to contact the anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, each TFC comprises an inner anode, an outer cathode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein the cross-section of the anode is a rounded non-circular shape with no sharp corners, wherein the cross-section is perpendicular to the longitudinal axis of the TFC, wherein the interconnect is in contact with the anode but not with the cathode, and the interconnect has a contact surface configured to contact the cathode of an adjacent TFC, wherein the cathode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

Also discussed herein are methods comprising applying a contact paste (contact paste) to a first Tubular Fuel Cell (TFC) and contacting a second TFC with the contact paste on opposite sides of the first TFC, wherein each of the first TFC and the second TFC comprises an inner cathode, an outer anode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein the cross-section of the cathode is a rounded non-circular shape with no sharp corners, wherein the cross-section is perpendicular to the longitudinal axis of the TFC, wherein the interconnect is in contact with the cathode but is not in contact with the anode, and the interconnect has a contact surface configured to contact the anode of an adjacent TFC, wherein the anode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, the contact paste is applied by immersion, coating, painting, spraying, spray pyrolysis or brushing, or a combination thereof. In one embodiment, the contact paste comprises gold, silver, platinum, nickel, iron, steel, stainless steel, chromium, cobalt, carbon, or inconel, or a combination thereof. In one embodiment, the contact paste comprises a material for an electrode in a fuel cell or a material for an interconnect in a fuel cell or both. In one embodiment, the TFC comprises a barrier layer between the cathode and the electrolyte or between the anode and the electrolyte or both.

In one embodiment, the rounded non-circular shape includes a rounded rectangle, rounded square, rounded hexagon, rounded trapezoid, rounded parallelogram, rounded pentagon, rounded triangle, rounded octagon, oval, ellipsoid, or rounded irregular shape. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 1, or no greater than 0.75, or no greater than 0.5. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 0.3, or no greater than 0.1, or no greater than 0.05. In one embodiment, the TFC has a length L and wherein the cross section has a characteristic length W, wherein the ratio of L/W is not less than 1, or not less than 2, or not less than 10, or not less than 100.

In one embodiment, the TFC includes a support in the cathode. In one embodiment, the support is in contact with the cathode. In one embodiment, the support is an integral part of the cathode. In one embodiment, the support and the cathode are made of the same material.

In one embodiment, the method includes heating the contact paste. In one embodiment, heating includes the use of electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, or combinations thereof. In one embodiment, the heating comprises oven heating, furnace heating, kiln heating, plasma heating, hot surface heating, or a combination thereof. In one embodiment, the heating is accomplished by conduction, convection, radiation, or a combination thereof. In one embodiment, the heating results in sintering, co-sintering, annealing, densification, curing, evaporating, drying, or a combination thereof.

Further discussed herein are methods comprising applying a contact paste to a first Tubular Fuel Cell (TFC) and contacting a second TFC with the contact paste on opposite sides of the first TFC, wherein each of the first TFC and the second TFC comprises an inner anode, an outer cathode, an electrolyte disposed between the anode and the cathode, and an interconnect, wherein the cross-section of the anode is a rounded non-circular shape without sharp corners, wherein the cross-section is perpendicular to the longitudinal axis of the TFC, wherein the interconnect is in contact with the anode but not in contact with the cathode, and the interconnect has a contact surface configured to contact the cathode of an adjacent TFC, wherein the cathode has a contact surface and a non-contact surface configured to contact the interconnect of another adjacent TFC.

In one embodiment, the contact paste is applied by immersion, coating, painting, spraying, brushing, or a combination thereof. In one embodiment, the contact paste comprises gold, silver, platinum, nickel, iron, steel, stainless steel, chromium, cobalt, carbon, or inconel, or a combination thereof. In one embodiment, the contact paste comprises a material for an electrode in a fuel cell or a material for an interconnect in a fuel cell or both. In one embodiment, the TFC comprises a barrier layer between the cathode and the electrolyte or between the anode and the electrolyte or both. In one embodiment, the ratio of the area of the contact surface of the interconnect to the area of the non-contact surface of the anode is no greater than 1, or no greater than 0.75, or no greater than 0.5, or no greater than 0.3, or no greater than 0.1, or no greater than 0.05. In one embodiment, the TFC has a length L and wherein the cross section has a characteristic length W, wherein the ratio of L/W is not less than 1, or not less than 2, or not less than 10, or not less than 100.

In one embodiment, the TFC includes a support in the anode. In one embodiment, the support is in contact with the anode. In one embodiment, the support is an integral part of the anode. In one embodiment, the support and the anode are made of the same material.

In one embodiment, the method includes heating the contact paste. In one embodiment, heating includes the use of electromagnetic radiation (EMR). In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, microwaves. In one embodiment, the heating comprises oven heating, furnace heating, kiln heating, plasma heating, hot surface heating, or a combination thereof. In one embodiment, heating is accomplished by conduction, convection, radiation, or a combination thereof. In one embodiment, the heating results in sintering, co-sintering, annealing, densification, curing, evaporating, drying, or a combination thereof.

Integrated heat exchanger

Disclosed herein are Electrochemical (EC) reactors, such as EC gas generators or Solid Oxide Reactors (SORs), comprising a first electrode, a second electrode, an electrolyte positioned between the first and second electrodes, and a first heat exchanger, wherein the first heat exchanger is in fluid communication with the first electrode. The minimum distance between the first electrode and the first heat exchanger is not greater than 10 cm. In some embodiments, the minimum distance is no greater than 5 cm. In other embodiments, the minimum distance is no greater than 1 cm. In other embodiments, the minimum distance is no greater than 5 mm. In other embodiments, the minimum distance is no greater than 1 mm. In one embodiment, the EC reactor comprises a second heat exchanger, wherein the second heat exchanger is in fluid communication with the second electrode. The minimum distance between the second electrode and the second heat exchanger is not greater than 10 cm. In some embodiments, the minimum distance is no greater than 5 cm. In other embodiments, the minimum distance is no greater than 1 cm. In other embodiments, the minimum distance is no greater than 5 mm. In other embodiments, the minimum distance is no greater than 1 mm.

In one embodiment, the first heat exchanger is adjacent to the first electrode, or alternatively, wherein the second heat exchanger is side by side or adjacent to the second electrode. One or more heat exchangers may be placed side-by-side with components in the EC reactor or above or below components (i.e., electrodes) of the EC reactor. Fig. 9B is an illustrative example in which an integrated multifluid heat exchanger containing 916 and 918 is located at the bottom of a repeating unit/stack in a fuel cell separated from anode 910 only by interconnect layer 920. In this case, the minimum distance between the heat exchanger and the repeat unit/stack is only the thickness of the interconnect, which is 1 mm or less, 0.5 mm or less, 200 microns or less, or in the range of about 100 nm to about 100 microns. In some embodiments, the first heat exchanger and the second heat exchanger are the same heat exchanger, wherein the heat exchangers form a multifluid heat exchanger. The EC reactor may comprise a solid oxide fuel cell, a solid oxide flow cell (solid oxide flow battery), an electrochemical gas generator, or an electrochemical compressor. The EC reactor may comprise a reformer upstream of the first electrode or a reformer in contact with the first electrode or a reformer in the first heat exchanger. The EC reactor may include two or more repeating units separated by an interconnect, wherein each repeating unit comprises a first electrode, a second electrode, and an electrolyte. Each repeating unit may include at least one heat exchanger adjacent to the repeating unit.

Also disclosed herein are EC reactors, such as Solid Oxide Reactors (SORs), comprising a stack of cells and a heat exchanger. The stack has a stack height and comprises a plurality of repeating units separated by interconnects, wherein each repeating unit comprises a first electrode, a second electrode, and an electrolyte between the first and second electrodes. The heat exchanger is in fluid communication with the stack, and wherein a minimum distance between the stack and the heat exchanger is no greater than 2 times the stack height, or no greater than half the stack height. The heat exchanger may be adjacent to the stack. The heat exchanger comprises at least 3 fluid inlets and at least 3 fluid channels, wherein each of the at least 3 fluid channels has a minimum dimension of no more than 30 mm. The stack or heat exchanger may also contain a reformer. The reformer may be constructed as a stack or a heat exchanger. In one embodiment, the interconnect does not contain a fluid dispersion element, and the electrode contains a fluid dispersion assembly or fluid channel.

In one embodiment, the EC reactor is in the form of a cassette (as shown in FIGS. 9A-9D). The cartridge may include a fuel inlet on a fuel side of the cartridge, an oxidant inlet on an oxidant side of the cartridge, at least one fluid outlet, wherein the fuel inlet has a width W _f The cartridge fuel side has a length L _f The oxidant inlet has a width W _o The oxidant side of the cartridge has a length L _o Wherein W is _f /L _f In the range of 0.1 to 1.0,0.1 to 0.9,0.2 to 0.9,0.5 to 0.9 or 0.5 to 1.0, and W _o /L _o In the range of 0.1 to 1.0,0.1 to 0.9,0.2 to 0.9,0.5 to 0.9 or 0.5 to 1.0. In some embodiments, the inlet and outlet are located on one surface of the cartridge, wherein the cartridge does not contain protruding flow channels located on the surface. The cassette may be removably secured to the mating surface and not welded or soldered to the mating surface. The cassette may be bolted or pressed to the mating surface. The mating surface may include a mating fuel inlet, a mating oxidant inlet, and at least one mating fluid outlet.

Also disclosed herein are EC reactor cassettes, such as Solid Oxide Reactor Cassettes (SORCs), comprising a first electrode, a second electrode, an electrolyte positioned between the first and second electrodes, and a heat exchanger, wherein the heat exchanger is in fluid communication with either the first electrode or the second electrode, or both. The minimum distance between the heat exchanger and the first or second electrode is no greater than 10 cm, or no greater than 5 cm, or no greater than 1 cm, or no greater than 5 mm, or no greater than 1 mm.

In one embodiment, the EC reactor cassette contains a reformer upstream of the first electrode or a reformer in contact with the first electrode or a heat exchanger. The EC reactor cartridge may include a fuel inlet located on a fuel side of the cartridge, an oxidant inlet located on an oxidant side of the cartridge, at least one fluid outlet, wherein the fuel inlet has a width W _f The fuel side of the cartridge has a length L _f Oxidant inlet utensilHaving a width W _o The oxidant side of the cartridge has a length L _o 。W _f /L _f The ratio of (2) is in the following range: 0.1 to 1.0,0.1 to 0.9,0.2 to 0.9,0.5 to 0.9 or 0.5 to 1.0, and W _o /L _o The ratio of (2) is in the following range: 0.1 to 1.0,0.1 to 0.9,0.2 to 0.9,0.5 to 0.9 or 0.5 to 1.0. The inlet and outlet may be located on one surface of the cartridge and wherein the cartridge does not contain protruding flow channels located on the surface. The EC reactor cassette may be removably secured to the mating surface and not welded or soldered to the mating surface.

Methods of forming an EC reactor, such as a Solid Oxide Reactor (SOR), are discussed herein that include forming a first electrode in a device, forming an electrolyte in the same device, forming a second electrode in the same device, and forming a heat exchanger in the same device, wherein the electrolyte is located between and in contact with the first electrode and the second electrode. The heat exchanger may be in fluid communication with either the first electrode or the second electrode, or both. The forming method may include one or more of material jetting, binder jetting, ink jet printing, aerosol jetting, aerosol printing, slot photopolymerization, powder layer fusion, material extrusion, directional energy deposition, sheet lamination, ultrasonic ink jet printing, direct (dry) powder deposition, or combinations thereof. Preferably, the forming is achieved by inkjet printing.

In one embodiment, the method of forming an EC reactor further comprises heating the EC reactor. The heating may be performed in situ. The heating may be performed using electromagnetic radiation (EMR). The method of forming an EC reactor may further comprise forming a plurality of repeating units and an interconnect between the repeating units, wherein the repeating units comprise a first electrode, an electrolyte, and a second electrode. In one embodiment, the formation of the repeating units and the interconnections occurs in the same device. In a preferred embodiment, the method includes in situ heating the repeating units and interconnects using EMR. In a preferred embodiment, the method further comprises forming a reformer. The reformer may be formed in the same apparatus.

In one embodiment, the interconnects in the EC reactor do not include fluid dispersion elements. In one embodiment, a method of forming an EC reactor includes forming a first template while forming a first electrode, wherein the first template is in contact with the first electrode; at least a portion of the first template is removed to form a channel in the first electrode. The method further includes forming a second template while forming a second electrode, wherein the second template is in contact with the second electrode; at least a portion of the second template is removed to form a channel in the second electrode. In one embodiment, the first electrode comprises a fluid dispersion assembly (FDC) or a fluid channel; wherein the second electrode comprises a fluid dispersion assembly (FDC) or a fluid channel.

In one embodiment, the EC reactor, such as the SOR, is formed into a cassette. The cartridge comprises a fuel inlet on the fuel side of the cartridge, an oxidant inlet on the oxidant side of the cartridge, at least one fluid outlet, wherein the fuel inlet has a width W _f The fuel side of the cartridge has a length L _f The oxidant inlet has a width W _o And the oxidant side of the cartridge has a length L _o 。W _f /L _f The ratio of (c) may be in the following range: 0.1 to 1.0,0.1 to 0.9,0.2 to 0.9,0.5 to 0.9 or 0.5 to 1.0, and W _o /L _o The ratio of (2) is in the following range: 0.1 to 1.0,0.1 to 0.9,0.2 to 0.9,0.5 to 0.9 or 0.5 to 1.0. In one embodiment, the inlet and outlet are located on one surface of the cartridge and the cartridge does not contain protruding flow channels located on said surface. In one embodiment, the cartridge is removably secured to the mating surface and is not welded or soldered to the mating surface. The cassette may be bolted or pressed to the mating surface. In one embodiment, the method includes forming a reformer upstream of the first electrode, or contacting the first electrode, or a reformer in a heat exchanger. The reformer may be formed in the same apparatus.

Also disclosed herein are methods comprising forming an EC reactor and a heat exchanger, wherein the reactor having a reactor height comprises a plurality of repeating units separated by interconnects, wherein each repeating unit comprises a first electrode, a second electrode, and an electrolyte positioned between the first and second electrodes. The heat exchanger may be in fluid communication with the stack, and wherein a minimum distance between the stack and the heat exchanger is no greater than 2 times the stack height, or no greater than half the stack height.

In one embodiment, the EC reactor stack, such as the SOR and the heat exchanger, is formed in the same apparatus. The method may include forming the stack and the heat exchanger into a cassette. The cassette may be removably secured to the mating surface and not welded or soldered to the mating surface.

Further discussed herein are methods comprising forming an EC reactor, such as an SOR, comprising a first electrode, a second electrode, an electrolyte between the first and second electrodes, and a heat exchanger. The heat exchanger may be in fluid communication with either the first electrode or the second electrode, or both. The minimum distance between the heat exchanger and the first electrode or the second electrode is no greater than 10 cm, no greater than 5 cm, no greater than 1 cm, no greater than 5 mm, or no greater than 1 mm. In some cases, the electrodes, electrolyte, and heat exchanger are formed in the same device. In some cases, the method further comprises forming the EC reactor into a cassette. The cassette may be removably secured to the mating surface and not welded or soldered to the mating surface.

Disclosed herein are methods comprising forming an EC reactor cassette comprising forming a first electrode, forming a second electrode, forming an electrolyte between the first and second electrodes, and forming a heat exchanger. In one embodiment, the heat exchanger is in fluid communication with either the first electrode or the second electrode, or both. In one embodiment, the electrodes, electrolyte and heat exchanger are formed in the same device. In one embodiment, the method includes forming a reformer upstream of the first electrode, or contacting the first electrode, or a reformer in a heat exchanger. In one embodiment, the reformers are formed in the same device.

Fischer-Tropsch process

The methods and systems of the present disclosure are suitable for preparing catalysts or catalyst composites, such as fischer-tropsch (FT) catalysts or catalyst composites. Disclosed herein are fischer-tropsch (FT) catalyst composites comprising a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is notLess than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In one embodiment, the catalyst comprises Fe, co, ni, or Ru. The substrate comprises Al ₂ O ₃ 、ZrO ₂ 、SiO ₂ 、TiO ₂ 、CeO ₂ Modified Al ₂ O ₃ Modified ZrO ₂ Modified SiO ₂ Modified TiO ₂ Modified CeO ₂ Gadolinium, steel, cordierite (2 MgO-2 Al) ₂ O ₃ -5SiO ₂ ) Aluminum titanate (Al) ₂ TiO ₅ ) Silicon carbide (SiC), all phases of alumina, yttria or scandia stabilized zirconia (YSZ), gadolinium oxide or samaria doped ceria, or combinations thereof. In one embodiment, the catalyst composite comprises a promoter, wherein the promoter comprises a noble metal, a metal cation, or a combination thereof. The accelerator may comprise B, la, zr, K, cu or a combination thereof. In one embodiment, the catalyst composite comprises fluid channels, or alternatively, a fluid dispersion assembly.

The FT reactor/system of the present disclosure is much smaller (e.g., 3-100 times smaller or 100+ times smaller for the same FT product yield) than conventional FT reactors/systems. By conventional methods of preparing FT catalysts, high catalyst to substrate ratios are not achievable. As such, in some embodiments, the FT reactor/system is miniaturized compared to conventional FT reactors/systems.

Also discussed herein are methods comprising depositing an FT catalyst to a substrate to form an FT catalyst composite, wherein the depositing comprises material jetting, binder jetting, inkjet printing, aerosol jetting or aerosol jet printing, slot photopolymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing, or a combination thereof. In one embodiment, the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In a preferred embodiment, the deposition method includes forming fluid channels in the catalyst composite, or alternatively, the fluid dispersion assembly.

Also discussed herein are systems comprising a fischer-tropsch (FT) reactor comprising a FT catalyst composite comprising a catalyst and a substrate, wherein the mass ratio between the catalyst and the substrate is not less than 1/100, or not less than 1/10, or not less than 1/5, or not less than 1/3, or not less than 1/1. In one embodiment, the catalyst comprises Fe, co, ni, or Ru. In one embodiment, the substrate comprises Al ₂ O ₃ 、ZrO ₂ 、SiO ₂ 、TiO ₂ 、CeO ₂ Modified Al ₂ O ₃ Modified ZrO ₂ Modified SiO ₂ Modified TiO ₂ Modified CeO ₂ Gadolinium, steel, cordierite (2 MgO-2 Al) ₂ O ₃ -5SiO ₂ ) Aluminum titanate (Al) ₂ TiO ₅ ) Silicon carbide (SiC), all phases of alumina, yttria or scandia stabilized zirconia (YSZ), gadolinium oxide or samaria doped ceria, or combinations thereof. In one embodiment, the catalyst composite comprises a promoter.

For example, the FT catalyst composite is formed by printing. The catalyst and substrate/support are made into an ink form comprising solvent and particles (e.g., nanoparticles). The ink optionally comprises a dispersant, a binder, a plasticizer, a surfactant, a co-solvent, or a combination thereof. The ink may be any kind of suspension. The ink may be treated by a mixing method such as ultrasonic or high shear mixing. In some cases, the iron ink is in an aqueous environment. In some cases, the iron ink is in an organic environment. The iron ink may also include an accelerator. The substrate/support may be a suspension or ink of alumina in an aqueous or organic environment. The substrate ink may be treated with a mixing process such as ultrasonic or high shear mixing. In some cases, the substrate ink includes an accelerator. In some cases, the ink as it is adds an accelerator in an aqueous or organic environment. In some cases, multiple inks are printed separately and sequentially. In some cases, multiple inks are printed separately and simultaneously, for example, by different printheads. In some cases, multiple inks are printed in combination as a mixture.

For example, the exhaust gas from the fuel cell comprises hydrogen, carbon dioxide, water, and optionally carbon monoxide. The exhaust gas is passed over an FT catalyst (e.g., an iron catalyst) to produce a synthetic fuel or lubricant. FT iron catalysts have the property of promoting either a water gas shift reaction or a reverse water gas shift reaction. The FT reaction occurs at a temperature in the range of 150-350 ℃ and at a pressure in the range of one to tens of atmospheres (e.g., 15 atm, or 10 atm, or 5 atm, or 1 atm). Additional hydrogen may be added to the waste stream to achieve a hydrogen to carbon oxides (carbon dioxide and carbon monoxide) ratio of not less than 2, or not less than 3, or between 2 and 3.

Fluid dispersion assembly

Fig. 12A shows an impermeable interconnect 1202 having a fluid dispersion assembly 1204, according to an embodiment of the present disclosure. Fig. 12B shows an impermeable interconnect 1202 having two fluid dispersion assemblies 1204, according to an embodiment of the disclosure. Fluid dispersion assembly 1204 is in contact with both sides (major faces) of interconnect 1202. As such, the interconnect is shared between two repeating units in an electrochemical reactor, such as in an EC gasifier. The fluid dispersion assembly 1204 is used to distribute a fluid, e.g., a reactive gas (e.g., methane, hydrogen, carbon monoxide, air, oxygen, etc.) in an electrochemical reactor. As such, conventional interconnects with vias are no longer required. The design and production of these conventional interconnects with channels is complex and expensive. According to the present disclosure, the interconnect is simply an impermeable layer that conducts or collects electrons, without fluid dispersion elements.

Fig. 12C-F schematically illustrate a segmented fluid dispersion assembly 1204 on top of an impermeable interconnect 1202, in accordance with an embodiment of the present disclosure. The segments may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The segments may be discontinuous. Fig. 13C shows segmented fluid dispersion assembly 1204 having a similar shape but a different size on impermeable interconnect 1202. Fig. 13D shows a segmented fluid dispersion assembly 1204 having a similar shape and similar dimensions on an impermeable interconnect 1202, in accordance with an embodiment of the present disclosure. Fig. 12E shows segmented fluid dispersion assembly 1204 having similar shapes and similar dimensions but closely packed on impermeable interconnect 1202, in accordance with an embodiment of the present disclosure. Fig. 12F shows segmented fluid dispersion assemblies 1204 having different shapes and different sizes on impermeable interconnects 1202, in accordance with an embodiment of the present disclosure. It is also contemplated that the segments have different compositions, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof.

Fig. 12G-I schematically illustrate an impermeable interconnect 1202 having a fluid dispersion assembly 1204, according to an embodiment of the disclosure. Different fluid inlet and outlet designs are also shown. The fluid dispersion assembly may have different densities, porosities, pore sizes, pore shapes, compositions, or permeabilities in different portions (e.g., in the transverse direction or in a direction perpendicular to the transverse direction) or combinations thereof. These degrees of variability provide control and adjustability of fluid flow in the fluid dispersion assembly. Fig. 12G shows an impermeable interconnect 1202 and a fluid dispersion assembly 1204 according to an embodiment of the present disclosure. Fig. 12H shows an impermeable interconnect 1202 and fluid dispersion assembly 1204 according to an embodiment of the present disclosure. Fig. 12I shows an impermeable interconnect 1202 and a fluid dispersion assembly 1204 according to an embodiment of the present disclosure. 1206 and 1208 in fig. 12G-I represent different inlet and outlet designs according to embodiments of the present disclosure. For each configuration, interconnect 1202 has mating inlets and outlets. In fig. 12I, 1206 represents a fluid inlet, and 1208 represents a fluid outlet. Fluid flow is indicated by arrows 1210. Fig. 12J shows an impermeable interconnect 1202 and a fluid dispersion assembly 1204, in accordance with an embodiment of the present disclosure. An alternative fluid flow design is further shown in fig. 12J, as indicated by the arrows. For example, fluid may flow through the fluid dispersion assembly from left to right; or the fluid may flow through the fluid dispersion assembly from front to back.

Fig. 12K shows a fluid dispersion assembly 1204 according to an embodiment of the disclosure. The fluid dispersion assembly 1204 design includes 4 corners labeled A, B, C and D. Position a includes fluid flow inlet 1212. Position B includes fluid flow outlet 1214.

An electrochemical reactor (e.g., a fuel cell) is discussed herein that includes an impermeable interconnect without a fluid dispersion element, an electrolyte, and a fluid dispersion assembly (FDC) between the interconnect and the electrolyte. In one embodiment, the fuel cell includes two FDCs. The two FDCs may be symmetrically placed to contact interconnects on opposite sides or opposite major faces thereof. As such, the interconnect shares two repeating units in the electrochemical reactor, each repeating unit comprising one of the two FDCs. The FDC may be foam, open cell foam, or contain a lattice structure.

In a preferred embodiment, the FDC is segmented, wherein the segments have different compositions, materials, shapes, sizes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The shape of the segments may include columns, hollow cylinders, cubes, rectangular cuboids, trigonal sided cubes, quadrilateral frustum, parallelepipeds, bi-triangular pyramids, quadrangle reverse wedges (quadrangle anti-wedge), pyramids, pentagonal pyramids, prisms, or combinations thereof.

In some embodiments, the FDCs have different densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof, wherein the densities, porosities, pore sizes, pore shapes, or permeabilities, or combinations thereof, are controlled. In some embodiments, density, porosity, pore size, pore shape, or permeability, or a combination thereof, is controlled to regulate fluid flow through the FDC. In other embodiments, the density, porosity, pore size, pore shape, or permeability, or a combination thereof, is controlled to result in 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 need not be uniform. The fluid flow may be increased or decreased depending on the reactivity of the FDC or the rate of reaction of the fluid in various portions of the FDC. Alternatively and/or in combination, the fluid flow may be increased or decreased depending on the fluid flow rate of the anode or cathode in the various portions of the FDC. Alternatively and/or in combination, fluid flow may be increased or decreased according to the reaction rate in the anode or cathode associated with or in contact with portions of the FDC.

In one embodiment, the density of FDC centers is higher. In one embodiment, the density of FDC centers is lower. In one embodiment, the porosity or permeability or pore throat size (pore throat size) is smaller toward the center of the FDC. In one embodiment, the porosity or permeability or pore throat size is greater toward the center of the FDC.

In one embodiment, at least a portion of the FDC is part of the anode or part of the cathode. In a preferred embodiment, the FDC is an anode or a cathode. In one embodiment, the impermeable interconnect has a thickness of no greater than 10 microns or no greater than 1 micron or no greater than 500 nm. In a preferred embodiment, the impermeable interconnect comprises an inlet and an outlet for a fluid. In a preferred embodiment, the fluid comprises a reactant of a fuel cell.

Also disclosed herein is a method of making a fuel cell comprising (a) forming an impermeable interconnect without a fluid dispersion element; (b) forming an electrolyte; (c) forming a fluid dispersion assembly (FDC); and (d) disposing the FDC between the interconnect and the electrolyte.

In one embodiment, the FDC is formed by creating a plurality 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 include pillars, hollow cylinders, cubes, rectangular cuboids, trigonal aspects, quadrilateral frustum, parallelepipeds, bicubic pyramids, tetragonal inverse wedges (pyramids), pyramids, pentagonal pyramids, prisms, or combinations thereof. The FDC may be a foam, an open cell foam; or contain a lattice structure.

In preferred embodiments, the method of forming the FDC comprises varying density, porosity, pore size, pore shape, permeability, or a combination thereof. In one embodiment, the method includes controlling the density, porosity, pore size, pore shape, permeability, or a combination thereof of the FDC. The method may include controlling the density, porosity, pore size, pore shape, or permeability of the FDC, or a combination thereof, to regulate the flow of fluid through the FDC. The method may include controlling the density, porosity, pore size, pore shape, permeability, or a combination 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 include controlling a density, porosity, pore size, pore shape, permeability, or a combination thereof of the FDC to cause a 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 need not be uniform. The fluid flow may be increased or decreased depending on the reactivity of the FDC or the rate of reaction of the fluid in various portions of the FDC. Alternatively and/or in combination, the fluid flow may be increased or decreased depending on the fluid flow rate of the anode or cathode in the various portions of the FDC. Alternatively and/or in combination, fluid flow may be increased or decreased according to the reaction rate in the anode or cathode associated with or in contact with portions of the FDC.

In one embodiment, step (c) includes altering the composition of the material used to form the FDC. In one embodiment, step (c) includes varying the particle size used to form the FDC. In one embodiment, step (c) includes heating different portions of the FDC to different temperatures. In one embodiment, the heating comprises electromagnetic radiation (EMR). In one embodiment, the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, or an electron beam.

In one embodiment, steps (a) - (d) or steps (b) - (d) are performed using Additive Manufacturing (AM). In various embodiments, AM includes extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition or lamination, or a combination thereof.

In one embodiment, the method of forming the FDC includes heating the fuel cell such that shrinkage of the FDC and electrolyte match, or shrinkage of the interconnect, FDC and electrolyte match. In a preferred embodiment, the heating includes EMR. In one embodiment, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser or electron beam, or a combination thereof. In a preferred embodiment, the heating is performed in situ. In preferred embodiments, the heating is performed for no more than 30 minutes, or no more than 30 seconds, or no more than 30 milliseconds.

In a preferred embodiment, at least a portion of the FDC is part of the anode or part of the cathode. In a preferred embodiment, the FDC is an anode or a cathode. In a preferred embodiment, the impermeable interconnect has a thickness of no greater than 10 microns or no greater than 1 micron or no greater than 500 nm. Preferably, the impermeable interconnect comprises an inlet and an outlet for fluid. More preferably, the fluid comprises a reactant of a fuel cell.

Channeled electrode (channeled electrode)

Disclosed herein are methods 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 a channel in the electrode material, such as in an EC gas generator. Fig. 13A shows a template 1300 for preparing a channeled electrode according to embodiments of the present disclosure. These templates may be removed by oxidation, melting, evaporation, reduction, or any suitable method after the electrochemical reactor is prepared or at the beginning of the reactor utilization.

In one embodiment, the channeled electrode material comprises NiO, YSZ, GDC, LSM, LSCF or a combination thereof. The channeled electrode material may include any of the materials previously described herein for use in a cathode or anode. In one embodiment, providing a template includes printing the template or assembling to form a precursor of the template. Providing the template includes polymerizing one or more monomers or photoinitiators or both. In one embodiment, the method comprises curing the monomer and/or oligomer by internal or external techniques. In various embodiments, the internal techniques include polymerization initiated by free radical molecules and/or initiated by in situ reduction/oxidation. In various embodiments, external techniques include photolysis, exposure to ionizing radiation, (ultra) sonication, and thermal decomposition to form an initiator species. In a preferred embodiment, the curing comprises UV curing. In one embodiment, the method includes adding a polymerization agent, wherein the polymerization agent includes a photoinitiator. In one embodiment, the polymerizer is printed on top of the monomers or within each monomer piece.

In one embodiment, providing the template includes dispersing the metal oxide particles in the monomer ink prior to printing the template. In one embodiment, the metal oxide comprises NiO, cuO, LSM (lanthanum strontium manganite), LSCF (lanthanum strontium cobalt ferrite), GDC (gadolinium doped ceria), SDC (samarium oxide doped ceria), or a combination thereof. In one embodiment, the monomers include alcohol, aldehyde, carboxylic acid, ester, and/or ether functional groups. In one embodiment, the template comprises NiO, cu (I) O, cu (II) O, organic compounds, photopolymers, or combinations thereof.

In one embodiment, removing at least a portion of the template includes heating, burning, solvent treatment, oxidation, reduction, or a combination thereof. In one embodiment, the combustion leaves no deposits and is not explosive. In one embodiment, the reduction is performed in a metal oxide and a porous template is created. In one embodiment, the method of providing a template includes in situ heating.

In one embodiment, the template and electrode material are printed sheet by sheet and a second sheet is printed atop the first sheet prior to heating the first sheet, wherein the heating removes at least a portion of the template. In one embodiment, the heating includes EMR. In one embodiment, the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam.

In one embodiment, the channels and electrode material form an electrode layer. In one embodiment, the channels have regular traces within the electrode layer. For example, the channels are parallel to each other. The channels may lead from one end, side or corner of the electrode layer to the opposite end, side or corner. The channel may run 90 degrees from one end, side or corner of the electrode to the other end, side or corner. The channels have random traces within the electrode layer. For example, the channels may have irregularly curved traces. The channel may have more than one entry point and more than one exit point. More than one entry point and more than one exit point are distributed across the electrode layer. The entry and exit points of the channels in the electrode layer may be located on either side of the electrode layer, including the upper surface or side and the lower surface or side.

In some embodiments, the volume fraction of template in the electrode layer is within the following range: 5% -95%, alternatively 10% -90%, alternatively 20% -80%, alternatively 30% -70%, alternatively 40% -60%. The volume fraction of channels in the electrode layer is in the following range: 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%. This total effective porosity of the electrode layer with channels is not less than the porosity of the electrode material. The electrode layer having the channels has a degree of torsion that is no greater than the natural degree of torsion of the electrode material.

In a preferred embodiment, the gas channel spans the height of the electrode layer. The gas channel may occupy a height less than the height of the electrode layer. For example, the electrode layer is about 50 microns thick. In one embodiment, the gas channel width is not less than 10 microns. In one embodiment, the gas channel width is not less than 100 microns.

Also discussed herein are methods 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 the interconnect. In a preferred embodiment, the steps are performed in any order. In a preferred embodiment, the method comprises repeating steps (a) - (d) in any order to form a stack or a repeat unit of a stack.

In one embodiment, the method includes (e) removing at least a portion of the first template and the second template to form channels in the first and second electrode layers. In one embodiment, the removing comprises heating, burning, solvent treatment, oxidation, reduction, or a combination thereof. In one embodiment, the removal is performed in situ. The removal may occur after printing the stack or repeating units of the stack. Removal may occur when the stack is caused to run. In one embodiment, printing is performed piece by piece and a second piece is printed on top of the first piece prior to heating the first piece, wherein the heating removes at least a portion of the template. The printing step includes material jetting, binder jetting, ink jet printing, aerosol jetting, or aerosol jet printing, or a combination thereof.

Further discussed herein are methods comprising (a) printing a first electrode layer; (b) printing an electrolyte layer; (c) printing a second electrode layer; and (d) printing the interconnect. In one embodiment, printing includes material jetting, binder jetting, inkjet printing, aerosol jetting, or aerosol jet printing. In a preferred embodiment, the steps are performed in any order. In a preferred embodiment, the method comprises repeating steps (a) - (d) in any order to form a stack or a repeat unit of a stack. Also disclosed herein are methods comprising aerosol spraying or aerosol jet printing an electrode layer, or an electrolyte layer, or an interconnect, or a combination thereof.

Fig. 13B is a cross-sectional view of a half-cell positioned between a first interconnect and an electrolyte, in accordance with an embodiment of the present disclosure. The stack in fig. 13B includes a bottom/first interconnect 1301, an optional layer 1302 containing a bottom interconnect material and a first electrode material, a first electrode segment 1303, a first filler material 1304 forming a first template, and an electrolyte 1305.

Fig. 13C is a cross-sectional view of a half-cell positioned between a second interconnect and an electrolyte, in accordance with an embodiment of the present disclosure. The half-cell includes an electrolyte 1305, a second electrode segment 1306, a filler material 1307 forming a second template, and a top/second interconnect 1308. The views shown in fig. 13B and 13C are perpendicular to each other.

Fig. 13D is a cross-sectional view of a half-cell positioned between a first interconnect and an electrolyte, in accordance with an embodiment of the present disclosure. The half-cell comprises a bottom interconnect 1301, an optional layer 1302 containing a bottom interconnect material and a first electrode material, a first electrode segment 1303, a first filler material 1304 forming a first template, an electrolyte 1305, and an optional protective layer (shield) 1409 of the first filler material when the first electrode is heated and/or sintered.

Fig. 13E is a cross-sectional view of a half-cell positioned between a second interconnect and an electrolyte, in accordance with an embodiment of the present disclosure. The half-cell includes an electrolyte 1305, a second electrode segment 1306, a filler material 1307 forming a second template, a top interconnect 1308, and an optional protective layer of the second filler material when the top interconnect is heated and/or sintered. The views shown in fig. 13D and 13E are perpendicular to each other.

In some embodiments, there is a layer (not shown) between 1307 and 1308 that contains the top interconnect material and the second electrode material. In some embodiments, 1305 represents an electrolyte having a barrier layer for the first electrode or the second electrode. 1309 represents an optional protective layer for the first filler when the first electrode is heated/sintered. 1310 represents an optional protective layer of a second filler as the top interconnect heats/sinters. In some cases, the electrolyte 1305 or electrolyte-blocking layer is in continuous contact with the first and second electrodes along opposite major faces thereof. The shape of the electrode segments and the filler in these cross-sectional views is merely representative and not exact. They may have any regular or irregular shape. When preparing an electrochemical reactor (e.g., a fuel cell stack or a gas generator), for example, by heating in a furnace, the filler and/or template is removed. Or alternatively, they are removed when the electrochemical reactor operation is initiated using the influence of oxidation, melting, evaporation, gasification, reduction, or a combination thereof, via hot gases/fluids passing therethrough. These removed fillers and/or templates become channels in the electrode. In various embodiments, there are multiple rows of channels in the electrode. For the illustrative example, the electrode is 25 microns thick with multiple channels having a height of 20 microns. For another illustrative example, the electrode is 50 microns thick, having 2 rows of multiple channels, each row of channels having a height of 20 microns. In various embodiments, the filler comprises carbon, graphite, graphene, cellulose, metal oxides, polymethyl methacrylate, nanodiamonds, or combinations thereof.

In one embodiment, a cell in an electrochemical reactor comprising an interconnect, a first electrode, an electrolyte, and a second electrode is fabricated by the method: providing an interconnect, depositing a first electrode material segment over 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 a first electrode, depositing an electrolyte material over the first electrode, sintering the electrolyte material to form an electrolyte, depositing a second electrode material over the electrolyte, thereby forming a plurality of valleys (valley) in the second electrode material, sintering the second electrode material to form a 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. In various embodiments, the deposition is performed using inkjet printing or ultrasonic inkjet printing. In various embodiments, sintering is performed using electromagnetic radiation (EMR). In some cases, the first and second filler materials absorb little EMR; the absorption is too small so that the filling material does not have a measurable change. In some cases, a protective layer is deposited to cover the first filler material or the second filler material, or both, such that the heating and/or sintering process of the top layer does not cause a measurable change in the first filler material or the second filler material, or both. In some cases, the protective layer comprises YSZ, SDC, SSZ, CGO, niO-YSZ, cu, cuO, cu ₂ O, LSM, LSCF, lanthanum chromite, stainless steel, LSGM or combinations thereof.

Double porosity electrode (dual porosity electrode)

Figures 14A-D show various embodiments of electrodes with dual porosities having 1, 2, or 3 layers shown in detail that may be used in electrochemical reactors, such as EC gasifiers. FIG. 14A schematically illustrates a fluid dispersion assembly segment in a first layer, in accordance with an embodiment of the disclosure; the first layer 1400 includes a fluid dispersion assembly section 1402. Segment 1402 may have different compositions, shapes, densities, porosities, pore sizes, pore shapes, permeabilities, or combinations thereof. The channel volume fraction (VFc) relative to the channel-containing layer 1400 is also shown. Electrodes in EC reactors comprising materials and channels are discussed herein, wherein the materials and channels form a first layer in an electrode having a first layer porosity. The material has a material porosity. The channel has a volume fraction VFc, which is the ratio of the channel volume to the first layer volume. The first layer porosity refers to the average porosity of the first layer as a whole. The first layer has a porosity at least 5% greater than the porosity of the material. VFc is within the following range: 0-99%, alternatively 1-30%, alternatively 10-90%, alternatively 5-50%, alternatively 3-30%, alternatively 1-50%. VFc is not less than 5%, or 10%, or 20%, or 30%, or 40%, or 50%.

Fig. 14B schematically illustrates a fluid dispersion assembly in a first layer and a second layer in an electrode, in accordance with an embodiment of the disclosure. The electrode embodiment in fig. 14B shows a first layer 1404 and a second layer 1406 of a fluid dispersion assembly segment 1405. As shown in fig. 14B, the segments 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 one embodiment, the 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 1406 may comprise the same material as in the first layer. The second layer 1406 may also include variations in composition, shape, density, porosity, pore size, pore shape, permeability, or combinations thereof in or perpendicular to the cross-machine direction.

Fig. 14D schematically illustrates fluid dispersion components in the first layer 1408 and the second layer 1412, according to an embodiment of the present disclosure. The electrode embodiment in fig. 14D is similar to the embodiment in fig. 14B. The electrode in fig. 14D includes a first layer 1408 that further includes a fluid dispersion assembly segment 1410, wherein the segment 1410 may have a different composition, shape, density, porosity, pore size, pore shape, permeability, or a combination thereof. The second layer 1412 may include the same materials as in the first layer. The second layer 1412 may also include variations in composition, shape, density, porosity, pore size, pore shape, permeability, or combinations thereof in or perpendicular to the cross-machine direction.

Fig. 14C schematically illustrates a fluid dispersion assembly in a first layer and second and third layers, according to an embodiment of the disclosure. The electrode embodiment in fig. 14C includes a first layer 1414, a second layer 1416, and a third layer 1418. In one embodiment, the second layer and the third layer are located on either side of the first layer. In one embodiment, the second layer and the third layer are in continuous contact with both sides of the first layer. The first layer 1414 can include segments 1420 having 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 the first layer. The second or third layer may also include variations in composition, shape, density, porosity, pore size, pore shape, permeability, or combinations thereof, in the cross-machine direction or perpendicular to the cross-machine direction.

In one embodiment, the first, second or third layer has a material porosity 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 one embodiment, the material porosity is not less than 25%, or 35%, or 45%.

In one embodiment, the thickness of the electrode is no greater than 10 a cm a, or 5 a cm a, or 1 a cm a. In one embodiment, the thickness of the electrode is no greater than 8 a mm a, or 5 a mm a, or 1 a mm a. In one embodiment, the thickness of the electrode is no greater than 100 microns, or 80 microns, or 60 microns.

In one embodiment, the contribution to permeability from the first layer of the channel is greater than the contribution to permeability from the first layer of the material. In one 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 one embodiment, the 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.

Disclosed herein is a method of making an Electrically Conductive Component (ECC) of an electrochemical reactor (e.g., a fuel cell), comprising: (a) Depositing a first composition comprising a first pore former having a first pore former volume fraction VFp1 on a substrate; (b) Depositing a second composition comprising a second pore former on the substrate, the second pore former having a second pore former volume fraction VFp2, wherein the first composition and the second composition form a first layer in ECC; and (c) heating the first layer, thereby rendering the first and second pore formers empty. In one embodiment, the VFp1 is within the following range: 0-100%, alternatively 10-90%, alternatively 30-70%, alternatively 50-100%, alternatively 90-100%. In one embodiment, VFp2 is within the following range: 0-100%, alternatively 0-70%, alternatively 25-75%, alternatively 30-60%. In one embodiment, the heating comprises a reduction reaction or an oxidation reaction, or both a reduction and an oxidation reaction.

Fig. 15 is an illustrative example of an electrode having dual porosities according to an embodiment of the present disclosure. Figure 15 shows an EC assembly 1500 comprising a channeled electrode having dual porosities. The apparatus 1500 includes an anode gas inlet 1501, an anode gas outlet 1502, a cathode gas inlet 1503, and a cathode gas outlet 1504. Exploded view 1505 is a view of a portion of the cathode layer. View 1506 is a close-up view of the cathode, where view 1506 represents a slice through the cathode layer composed of cathode 1507. The cathode 1507 is a porous cathode formed using a microporous pore former. Channels 1508 represent the channels formed by the macroporous pore formers.

In one embodiment (a) and (b) are achieved by printing, or by extrusion, or by Additive Manufacturing (AM), or by cast molding, or by spray coating, or by deposition, or by sputtering, or by screen printing. In one embodiment, the additive manufacturing includes extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, lamination.

In one embodiment, the first and second pore formers are the same. In one embodiment, the first pore former and the second pore former are different. In one embodiment, the average diameter of the first or second pore formers is in the range of 10 nm to 1 mm, or 100 nm to 100 microns, or 500 nanometers to 50 microns. In one embodiment, the first pore former or the second pore former has a particle size distribution. In one embodiment, the first or second pore formers comprise carbon, graphite, polymethyl methacrylate (PMMA), cellulose, metal oxide, or a combination thereof.

In one embodiment, the method includes repeating (a) and (b) to form a second layer in the ECC; and heating the second layer. In one embodiment, the heating of the second layer is performed simultaneously with the heating of the first layer. In one embodiment, the heating of the second layer is performed at a different time than the heating of the first layer. In one embodiment, heating the second layer and heating the first layer has at least partially overlapping time periods. In one embodiment, the method comprises repeating (a) and (b) to form a third layer in the ECC; and heating the third layer. In one embodiment, the second layer and the third layer are located on either side of the first layer. In one embodiment, the heating of the first, second and third layers is simultaneous. Alternatively, the first, second and third layers are heated at different times. In one embodiment, the heating of the first, second and third layers has overlapping time periods. In one embodiment, the first, second or third layer is heated more than once.

In one embodiment, at least a portion of the void space created by the second pore former or the first pore former or both becomes a channel in the first layer. In one embodiment, the channel has a volume fraction VFc, which is the ratio of the channel volume to the first layer volume. In one embodiment, the VFc is within the following range: 0-99%, alternatively 1-30%, alternatively 10-90%, alternatively 5-50%, alternatively 3-30%, alternatively 1-50%. In one embodiment, the VFc is not less than 5%, or 10%, or 20%, or 30%, or 40%, or 50%.

In one embodiment, VFp1 is different from VFp2. In one embodiment, the first layer has dual porosity, material porosity and layer porosity. In one embodiment, the material porosity is within the following range: 20-60%, or 30-50%, or 30-40%, or 25-35%. In one embodiment, the material porosity is not less than 25%, or 35%, or 45%.

In one embodiment, the thickness of the ECC is no greater than 10 a cm a, or 5 a cm a, or 1 a cm a. In one embodiment, the thickness of the ECC is no greater than 8 mm, or 5 mm, or 1 mm. In one embodiment, the thickness of the ECC is no greater than 100 microns, or 80 microns, or 60 microns.

In one embodiment, the first layer comprises channels and material after (c), wherein the contribution to permeability from the first layer of channels is greater than the contribution to permeability from the first layer of material. In one 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 one embodiment, the 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.

A method is discussed herein comprising: (a) providing a first material to an Additive Manufacturing Machine (AMM); (b) providing a second material to the AMM; (c) mixing the first material and the second material into a mixture; and (d) forming the mixture into a part. In one embodiment, the first material or the second material is a gas, or a liquid, or a solid, or a gel.

In one embodiment, the additive manufacturing includes extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, lamination. In one embodiment, the 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. In one embodiment, steps (c) and (d) occur continuously.

In one embodiment, step (c) includes varying the ratio of the first material to the second material in the mixture. In one embodiment, the ratio of the first material to the second material in the mixture is varied in situ. In one embodiment, the ratio of the first material to the second material in the mixture is changed in real time. In one embodiment, the ratio of the first material to the second material in the mixture is continuously varied. In one embodiment, the ratio of the first material to the second material in the mixture is varied according to the composition distribution (composition profile). In one embodiment, the ratio of the first material to the second material in the mixture is changed according to a manual algorithm, a computational algorithm, or a combination thereof. In one embodiment, the ratio of the first material to the second material in the mixture is varied by controlling the material flow rate or pumping rate.

In one embodiment, step (d) comprises placing the mixture in a pattern on a substrate. In one embodiment, step (d) comprises placing the mixture according to a predefined technical specification.

In one embodiment, the formed components have different properties. In one embodiment, the property comprises strength, weight, density, electrical properties, electrochemical properties, or a combination thereof. In various embodiments, the formed component has superior properties, such as strength, density, weight, electrical or electrochemical properties, or a combination thereof, when compared to similar components formed by different methods.

In one embodiment, step (d) comprises depositing the mixture on a substrate. In one embodiment, mixing is performed prior to deposition, during deposition, or after deposition. In one embodiment, the mixing is performed in AMM, either in air or on a substrate. In one embodiment, mixing is performed by advection, dispersion, diffusion, melting, fusion, pumping, stirring, heating, or a combination thereof.

Disclosed herein is an Additive Manufacturing Machine (AMM) 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 the AMM is configured to form the mixture into a part. In one embodiment, the first material or the second material is a gas, or a liquid, or a solid, or a gel.

In one embodiment, the AMM is configured for extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination. In one embodiment, the 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 bond jetting.

In one embodiment, the mixer is configured to continuously mix the first material and the second material, and the AMM forms the mixture into a part. In one embodiment, the mixer is configured to change the ratio of the first material to the second material in the mixture. In one embodiment, the mixer is configured to change the ratio of the first material to the second material in the mixture in situ. The mixer may be configured to change the ratio of the first material to the second material in the mixture in real time. In one embodiment, the mixer may be configured to continuously vary the ratio of the first material to the second material in the mixture. In one embodiment, the mixer is configured to vary the ratio of the first material to the second material in the mixture according to the composition distribution. In one embodiment, the mixer is configured to change the ratio of the first material to the second material in the mixture according to a manual algorithm, a computational algorithm, or a combination thereof. In one embodiment, the mixer is configured to vary the ratio of the first material to the second material in the mixture by controlling the material flow rate or pumping rate.

In one embodiment, the AMM is configured to place the mixture in a pattern on a substrate. In one embodiment, the AMM is configured to place the mixture in accordance with a predefined technical specification.

In one embodiment, the formed components have different properties. In one embodiment, the property comprises strength, weight, density, electrical properties, electrochemical properties, or a combination thereof. In various embodiments, the formed component has superior properties, such as strength, density, weight, electrical or electrochemical properties, or a combination thereof, when compared to similar components formed using different devices.

In one embodiment, the AMM is configured to deposit the mixture on a substrate. In one embodiment, mixing is performed prior to deposition, during deposition, or after deposition. In one embodiment, the mixing is performed in AMM, either in air or on a substrate. In one embodiment, mixing is performed by advection, dispersion, diffusion, melting, fusion, pumping, stirring, heating, or a combination thereof.

Integrated deposition and heating

Disclosed herein are methods comprising depositing a composition on a substrate sheet by sheet (this may also be referred to as a line by line deposition) to form an object; in situ heating of the object using electromagnetic radiation (EMR); wherein the composition comprises a first material and a second material, wherein the second material has a higher EMR absorptivity than the first material. In various embodiments, the heating may cause the following effects: drying, curing, sintering, annealing, sealing, alloying, evaporating, reconstructing, foaming or a combination thereof. In some embodiments, the peak wavelength of the EMR is in the range of 10 to 1500 nm, and the minimum energy density is 0.1 joules/cm ² Wherein the peak wavelength is based on radiation relative to wavelength. In some embodiments, the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, or an electron beam.

Fig. 16 shows a system for integrated deposition and heating using electromagnetic radiation (EMR) in accordance with an embodiment of the disclosure. The system 1600 may be used to assemble an electrochemical reactor, such as a fuel cell or an EC gas generator. Fig. 16 also shows a system 1600 according to an embodiment of the present disclosure, which is an object 1603 on a receiver 1604 formed by a deposition nozzle 1601 and EMR 1602 for in situ heating. The receiver 1604 may be a stage that moves and may further receive deposition, heating, radiation, or a combination thereof. The receptacle 1604 may also be referred to as a chamber, where the chamber may be completely enclosed, partially enclosed, or completely open to the atmosphere.

In some embodimentsThe first material comprises Yttria Stabilized Zirconia (YSZ), 8YSZ (8 mol% YSZ powder), yttrium, zirconium, gadolinium oxide doped ceria (GDC or CGO), samarium oxide doped ceria (SDC), scandium oxide stabilized zirconia (SSZ), lanthanum Strontium Manganite (LSM), lanthanum cobalt ferrite (LSCF), lanthanum Strontium Cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel, niO-YSZ, cu-CGO, cu ₂ O, cuO, cerium, copper, silver, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof. In other embodiments, the first material comprises YSZ, SSZ, CGO, SDC, niO-YSZ, LSM-YSZ, CGO-LSCF, doped lanthanum chromite, stainless steel, or combinations thereof. In some embodiments, the second material comprises carbon, nickel oxide, nickel, silver, copper, CGO, SDC, niO-YSZ, niO-SSZ, LSCF, LSM, doped lanthanum chromite, ferritic steel, or combinations thereof. The first material may include any of the electrode materials previously disclosed herein.

In some embodiments, object 1603 comprises a catalyst, catalyst support, catalyst composite, anode, cathode, electrolyte, electrode, interconnect, seal, fuel cell, electrochemical gas generator, electrolyzer, electrochemical compressor, reactor, heat exchanger, vessel, or a combination thereof.

In some embodiments, the second material may be deposited in the same sheet as the first material. In other embodiments, the second material may be deposited in a sheet adjacent to another sheet containing the first material. In some embodiments, the heating may remove at least a portion of the second material. In a preferred embodiment, the heating leaves minimal residue of the second material so that there is no significant residue that would interfere with subsequent steps during the process or operation of the build device. More preferably, this leaves no measurable residual portion of the second material.

In some embodiments, the second material may add thermal energy to the first material during heating. In other embodiments, the radiation absorbance of the second material is at least 5 times that of the first material; the second material has a radiation absorbance at least 10 times that of the first material; the second material has a radiation absorbance at least 50 times that of the first material; or the second material has a radiation absorption rate of at least 100 times that of the first material.

In some embodiments, the second material may have a peak absorption wavelength of not less than 200 nm, or 250 nm, or 300 nm, or 400 nm, or 500 nm. In other embodiments, the peak absorption wavelength of the first material is no greater than 700 nm, or 600 nm, or 500 nm, or 400 nm, or 300 nm. In other embodiments, the peak wavelength of EMR is no less than 200 nm, or 250 nm, or 300 nm, or 400 nm, or 500 nm.

In some embodiments, the second material may include carbon, nickel oxide, nickel, silver, copper, CGO, niO-YSZ, LSCF, LSM, ferritic steel, other metal oxides, or combinations thereof. In some cases, the ferritic steel is Crofer 22 APU. In some embodiments, the first material comprises YSZ, CGO, niO-YSZ, LSM-YSZ, other metal oxides, or combinations thereof. In one embodiment, the second material comprises LSCF, LSM, carbon, nickel oxide, nickel, silver, copper, or steel. In some embodiments, the carbon comprises graphite, graphene, carbon nanoparticles, nanodiamonds, or a combination thereof. The second material may include any of the electrode materials previously disclosed herein.

In some embodiments, the deposition method comprises material jetting, binder jetting, inkjet printing, aerosol jetting, aerosol jet printing, slot photopolymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing, or combinations thereof.

In some embodiments, the deposition method further comprises one or more of the following steps: the distance of the EMR from the receiver, the EMR energy density, the EMR spectrum, the EMR voltage, the EMR exposure time, the EMR exposure area, the EMR exposure volume, the EMR pulse frequency, the EMR exposure repetition number are controlled. In one embodiment, the object does not change position between the depositing and heating steps. In one embodiment, the power output of the EMR is no less than 1W, or 10W, or 100W, or 1000W.

Also disclosed herein is 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. In some cases, the receiver is configured such that it receives a deposit for a first period of time, moving to a different location in the system to receive EMR exposure for a second period of time.

The following detailed description describes the production of Solid Oxide Fuel Cells (SOFCs) for illustrative purposes. As will be appreciated by those skilled in the art, the method and production method are applicable to all fuel cell types. As such, production of all fuel cell types is within the scope of the present disclosure.

Additive manufacturing

Additive Manufacturing (AM) refers to a set of techniques that combine materials, typically piece by piece or layer by layer, to produce an object. AM is in contrast to subtractive manufacturing, which involves removing a portion of material by machining, cutting, grinding or etching away. AM may also be referred to as additive fabrication, additive processes, additive technology, additive layer production, or free-form fabrication. Some examples of AM are extrusion, photopolymerization, powder layer 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. 3D printers are a type of AM machine (AMM). Inkjet printers or ultrasonic inkjet printers are other examples of AMMs.

In a first aspect, the invention is a method of making an electrochemical reactor, such as an EC gas generator or fuel cell, comprising: (a) producing an anode using AMM; (b) generating an electrolyte using AMM; and (c) preparing a cathode using AMM. In a preferred embodiment, the anode, electrolyte and cathode are assembled into a fuel cell using AMM, except for other steps that are accomplished without AMM. In a preferred embodiment, only AMM is used to form the fuel cell. In other embodiments, steps (a), (b) and (c) do not include cast molding and screen printing. In one embodiment, the method of assembling a fuel cell using AMM does not include compression in the assembly. In other embodiments, the layers are deposited layers on top of one another in a stepwise fashion, thereby completing the assembly at the same time as the deposition. The methods described herein are useful in the preparation of flat-plate fuel cells. The methods described herein are also useful in preparing fuel cells where the current is perpendicular to the electrolyte in the transverse direction when the fuel cell is in use.

In one embodiment, the interconnect, anode, electrolyte, and cathode are formed layer by layer, e.g., printed layer by layer. It is important to note that the order in which these layers are formed may be varied within the scope of the present invention. In other words, either the anode or the cathode may be formed before the other. Naturally, an electrolyte is formed so as to be between the anode and the cathode. The barrier layer, catalyst layer and interconnect are formed so as to be in place within the fuel cell to perform their functions.

In some embodiments, each of the interconnect, anode, electrolyte, and cathode has 6 faces. In a preferred embodiment, the anode is printed onto and in contact with the interconnect; printing an electrolyte onto and in contact with the anode; the cathode is printed onto and in contact with the electrolyte. Each print may be sintered, for example, using EMR. As such, the assembly process and the formation process are simultaneous, which is not possible by conventional methods. Furthermore, by the preferred embodiment, the desired electrical contact and air tightness are also achieved at the same time. In contrast, conventional fuel cell assembly processes accomplish this by extrusion or compression of the fuel cell components or layers. The extrusion and compression processes can cause undesirable cracking in the fuel cell layers.

In some embodiments, the AM method includes preparing at least one barrier layer using AMM. In a preferred embodiment, at least one barrier layer may be located between the electrolyte and the cathode or between the electrolyte and the anode or both. In other embodiments, AMM may be used, with at least one barrier layer assembled using an anode, electrolyte, and cathode. In some embodiments, no barrier layer is required or used in the fuel cell.

In some embodiments, the AM method includes fabricating the interconnect using AMM. In other embodiments, AMM may be used, with anode, electrolyte, and cathode assembly interconnects. In some embodiments, the AMM forms a catalyst and introduces the catalyst into the fuel cell.

In some embodiments, the anode, electrolyte, cathode, and interconnect are prepared at a temperature greater than 100 ℃. In some embodiments, the AM method includes heating a fuel cell, wherein the fuel cell includes an anode, an electrolyte, a cathode, an interconnect, and optionally at least one barrier layer. In some embodiments, the fuel cell comprises a catalyst. In some embodiments, the method includes heating the fuel cell to a temperature greater than 500 ℃. In some embodiments, the fuel cell is heated using one or both of EMR or oven curing.

In a preferred embodiment, AMM utilizes a multi-nozzle additive manufacturing method. In a preferred embodiment, the multi-nozzle additive manufacturing method includes nanoparticle jetting. In some embodiments, the first nozzle delivers a first material, the second nozzle delivers a second material, and the third nozzle delivers a third material. In some embodiments, the fourth material particles are placed in contact with the partially constructed fuel cell and bonded to the partially constructed fuel cell using laser, photoelectric effect, light, heat, polymerization, or bonding. In one embodiment, the anode, cathode, or electrolyte comprises a first, second, third, or fourth material. In a preferred embodiment, AMM implements a plurality of AM techniques. In various embodiments, the AM techniques include one or more of extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, or lamination. In various embodiments, AM is a deposition technique that includes material jetting, binder jetting, inkjet printing, aerosol jetting or aerosol jet printing, slot photopolymerization, powder layer fusion, material extrusion, directed energy deposition, sheet lamination, ultrasonic inkjet printing, or a combination thereof.

Further described herein is an AM method of making a fuel cell stack comprising: (a) producing an anode using an Additive Manufacturing Machine (AMM); (b) generating an electrolyte using AMM; (c) preparing a cathode using AMM; (d) preparing an interconnect using AMM; wherein the anode, electrolyte, cathode and interconnect form a first fuel cell; (e) Repeating steps (a) - (d) to produce a second fuel cell; and (f) assembling the first fuel cell and the second fuel cell into a fuel cell stack.

In some embodiments, the first fuel cell and the second fuel cell are formed from an anode, an electrolyte, a cathode, and an interconnect using AMM. In one embodiment, the fuel cell stack is formed using only AMM. In other embodiments, steps (a) - (f) do not include one or both of cast molding and screen printing.

In some embodiments, the AM method includes preparing at least one barrier layer using AMM. In some embodiments, for the first fuel cell and the second fuel cell, at least one barrier layer is located between the electrolyte and the cathode or between the electrolyte and the anode or both.

In some embodiments, steps (a) - (d) are performed at a temperature greater than 100 ℃. In other embodiments, steps (a) - (d) are performed at a temperature in the range of 100 ℃ to 500 ℃. In some embodiments, the AMM prepares and introduces the catalyst into the fuel cell stack.

In some embodiments, the AM method includes heating the fuel cell stack. In one embodiment, the AM process includes heating the fuel cell stack to a temperature greater than 500 ℃. In some embodiments, EMR and/or oven curing is used to heat the fuel cell stack. In some embodiments, the laser has a laser beam, wherein the laser beam expands to produce a heating zone having a uniform power density. In some embodiments, the laser beam is expanded by using one or more mirrors. In some embodiments, each layer of the fuel cell may be individually cured 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 EMR is cured, assembled with the second fuel cell, and then the second fuel cell EMR is cured. In other embodiments, the first fuel cell is assembled with the second fuel cell, and then the first fuel cell and the second fuel cell are cured by EMR alone. In some embodiments, the first fuel cell and the second fuel cell may be cured separately by EMR, and then the first fuel cell and the second fuel cell are assembled to form a fuel cell stack. In some embodiments, the first fuel cell is assembled with the second fuel cell to form a fuel cell stack, which can then be cured by EMR.

Also discussed herein are AM methods of making a plurality of fuel cells comprising (a) simultaneously producing a plurality of anodes using an Additive Manufacturing Machine (AMM); (b) simultaneously producing a plurality of electrolytes using AMM; and (c) simultaneously preparing a plurality of cathodes using AMM. In a preferred embodiment, the anode, electrolyte and cathode are assembled simultaneously into a fuel cell using AMM. In other preferred embodiments, only AMM is used to form the fuel cell.

In some embodiments, the method includes preparing at least one barrier layer for each of a plurality of fuel cells simultaneously using 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. In a preferred embodiment, AMM may be used for each fuel cell, with at least one barrier layer assembled using an anode, electrolyte and cathode.

In some embodiments, the method includes preparing an interconnect using AMM simultaneously for each of a plurality of fuel cells. For each fuel cell, AMM may be used, with anode, electrolyte and cathode assembly interconnects. In other embodiments, for each of a plurality of fuel cells, the AMM forms a catalyst simultaneously and introduces the catalyst into each fuel cell. In other embodiments, the heating of each layer or the heating of a combination of layers of multiple fuel cells is performed simultaneously. The plurality of fuel cells may include two or more fuel cells.

In a preferred embodiment, the AMM uses two or more different nozzles to simultaneously jet or print different materials. For the first example, while in AMM, the first nozzle deposits the anode layer of fuel cell 1, the second nozzle deposits the cathode layer of fuel cell 2 and the third nozzle deposits the electrolyte of fuel cell 3. For the second example, while in AMM, the first nozzle deposits the anode of fuel cell 1, the second nozzle deposits the cathode of fuel cell 2, the third nozzle deposits the electrolyte of fuel cell 3 and the fourth nozzle deposits the interconnect of fuel cell 4.

Disclosed herein are Additive Manufacturing Machines (AMMs) comprising a chamber in which fuel cell production is performed. The chamber is capable of withstanding temperatures of at least 100 ℃. In one embodiment, the chamber is capable of producing a fuel cell. The chamber is capable of heating the fuel cell in situ while the fuel cell assembly is being deposited.

In some embodiments, the heating chamber may be heated by laser, electromagnetic waves/electromagnetic radiation (EMR), thermal fluid, or a heating element associated with the chamber, or a combination thereof. The heating element may comprise a heating surface, a heating coil or a heating rod. In other embodiments, the chamber may be configured to apply pressure to the interior of the fuel cell. The pressure may be applied by a moving element associated with the chamber. The moving element may move the punch or the piston. In some embodiments, the 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 as necessary.

In some cases, the chamber may be closed. In some cases, the chamber may be sealed. In some cases, the chamber may be open to the ambient atmosphere or to a controlled atmosphere. In some cases, the chamber may be a platform without top and side walls.

Referring to fig. 16, a system 1600 includes a deposition nozzle or material ejection nozzle 1601, an EMR source 1602 (e.g., a xenon lamp), an object 1603 being formed, and a chamber or receiver 1604 that is part of an AMM. As shown in fig. 16, the chamber or receiver 1604 is configured to receive deposition from a nozzle and radiation from an EMR source 1602. In various embodiments, the deposition nozzle 1601 may be movable. In various embodiments, the chamber or receiver 1604 may be movable. In various embodiments, the EMR source 1602 is movable. In various embodiments, 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 generator, an electrolyzer, an electrochemical compressor, a reactor, a heat exchanger, a vessel, or a combination thereof.

AM techniques suitable for the present disclosure include extrusion, photopolymerization, powder layer fusion, material jetting, binder jetting, directed energy deposition, and lamination. In some embodiments, extrusion may be used for AM. Extrusion AM involves spatially controlled deposition of a material (e.g., a thermoplastic). In the present disclosure, extruded AM may also be referred to as fuse fabrication (FFF) or Fused Deposition Modeling (FDM).

In some embodiments, for the methods of the present disclosure, AM comprises photopolymerization (i.e., stereolithography (SLA)). SLA includes spatially defined curing of a photoactive liquid ("photosensitive resin") using a scanning laser or high resolution projected image and conversion of the photoactive liquid to a crosslinked solid. Photopolymerization may produce features having details and dimensions in the micrometer to meter scale.

In some embodiments, AM comprises powder layer fusion (PBF). The PBF AM method builds objects by melting a powder raw material, such as a polymer or a metal. The PBF process is initiated by distributing a thin layer of powder within the build area. Then, one layer of cross-section is melted at a time, most often using a laser, electron beam or intense infrared lamp. In some embodiments, the metal PBF may use Selective Laser Melting (SLM) or Electron Beam Melting (EBM). In other embodiments, the PBF of the polymer may use Selective Laser Sintering (SLS). In various embodiments, the SLS system may print thermoplastic polymer materials, polymer composites, or ceramics. In various embodiments, the SLM system may be adapted to a variety of pure metals and alloys, where the alloys are compatible with the rapid solidification that occurs in the SLM.

In some embodiments, AM may include material jetting. AM through material ejection may be accomplished by spatially controlled deposition of droplets (or droplets) of material. In various embodiments, 3-dimensional (3D), 2-dimensional (2D) material jetting, or both, are implemented. In a preferred embodiment, the 3D jetting is done layer by layer. In a preferred embodiment, print preparation translates the technical requirements of computer-aided design (CAD) and material composition, color and other variables into print instructions for each layer. The binder jetting AM comprises inkjet deposition of a liquid binder on the powder layer. In some cases, binder jetting is combined with other AM methods, such as, for example, powder diffusion to produce a powder layer (similar to SLS/SLM) and inkjet printing.

In some embodiments, the AM includes Directional Energy Deposition (DED). Instead of using a powder layer as discussed above, the DED method uses a directed powder flow or wire feed (wire feed), and an energy-intensive source such as a laser, arc or electron beam. In a preferred embodiment, the DED is a direct write method in which the material deposition location is determined by moving the deposition head, which enables large metal structures to be built without the limitations of powder layers.

In some embodiments, AM comprises laminated AM or layered physical manufacturing (LOM). In a preferred embodiment, successive layers of sheet material are continuously bonded and cut to form 3D structures.

Conventional methods of producing a fuel cell stack may include over 100 steps. These steps may include, but are not limited to, milling, grinding, filtering, analyzing, mixing, bonding, evaporating, aging, drying, extruding, diffusing, casting, screen printing, stacking, heating, extruding, sintering, and compressing. The methods disclosed herein describe the production of a fuel cell or fuel cell stack using an AMM.

The AMM of the present disclosure preferably performs both extrusion and inkjet to produce a fuel cell or fuel cell stack. Extrusion can be used to produce thicker layers for fuel cells such as anodes and/or cathodes. Inkjet can be used to produce thin layers of fuel cells. Inkjet can be used to produce electrolytes. The AMM may be operated within a temperature range sufficient to enable curing in the AMM itself. These temperatures range from 100℃or more, from 100 to 300℃or from 100 to 500 ℃.

As a preferred example, all the fuel cell layers are formed and assembled by printing. The materials used to prepare the anode, cathode, electrolyte, and interconnect may be made in the form of inks containing solvents and particles (e.g., nanoparticles), respectively. There are two types of ink formulations-aqueous and non-aqueous. In some cases, the aqueous ink includes an aqueous solvent (e.g., water, deionized water), particles, a dispersant, and a surfactant. In some cases, the aqueous ink comprises an aqueous solvent, particles, a dispersant, a surfactant, but does not comprise a polymeric binder. The aqueous ink may optionally include a co-solvent, such as an organic miscible solvent (methanol, ethanol, isopropanol). These co-solvents preferably have a boiling point lower than that of water. The dispersant may be an electrostatic dispersant, a stereochemical dispersant, an ionic dispersant or a nonionic dispersant or a combination thereof. The surfactant may preferably be nonionic, such as an alcohol alkoxylate or alcohol ethoxylate. The non-aqueous ink may include organic solvents (e.g., methanol, ethanol, isopropanol, butanol) and particles.

For example, CGO powder is mixed with water to form an aqueous ink that also contains added dispersant and surfactant, but does not contain added polymeric binder. The CGO fraction (expressed herein as weight percent (wt%)) on a mass basis is in the range of 10 wt% to 25 wt%. For example, the CGO powder is mixed with ethanol to form a non-aqueous ink that also includes polyvinyl butyral having a CGO fraction in the range of 3 wt% to 30 wt%. For example, LSCF is mixed with n-butanol or ethanol to form a non-aqueous ink that further comprises polyvinyl butyral having an LSCF fraction in the range of 10 wt% to 40 wt%. For example, YSZ particles are mixed with water to form an aqueous ink that also includes added dispersant and surfactant, but does not include added polymeric binder. YSZ fraction is in the range of 3 wt% to 40 wt%. For example, niO particles are mixed with water to form an aqueous ink that also contains added dispersant and surfactant, but does not contain added polymeric binder, with NiO fraction in the range of 5 wt% to 25 wt%.

For example, for the cathode of a fuel cell, 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. For example, LSCF is deposited (e.g., printed) in layers. By EMR, a xenon lamp can be used to irradiate the LSCF layer to sinter the LSCF particles. The xenon flash lamp may be 10 kW units with a total exposure time of 1000 ms applied at 400V voltage and 10 Hz frequency.

For example, for an electrolyte, YSZ particles are mixed with a solvent, where the solvent is water (e.g., deionized water) or an alcohol (e.g., butanol) or a mixture of alcohols. Organic solvents other than alcohols may also be used in other examples. For interconnects, metal particles (e.g., silver nanoparticles) are dissolved in a solvent, where the solvent may include water (e.g., deionized water) and an organic solvent. The organic solvent may include mono-, di-, or tri-ethylene glycol or higher ethylene glycol, propylene glycol, 1, 4-butanediol or ethers of these glycols, thiodiglycol, glycerol and ethers and esters thereof, polyglycerol, mono-, di-, and tri-ethanolamine, propanolamine, N-dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethylimidazolidone, methanol, ethanol, isopropanol, N-propanol, diacetone alcohol, acetone, methyl ethyl ketone, or propylene carbonate, or combinations thereof. For the barrier layer in the fuel cell, the CGO particles are dissolved in a solvent, where the solvent may be water (e.g., deionized 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 a barrier to LSCF. YSZ may also be used as a barrier to LSM. In some cases, for aqueous inks in which water is a solvent, a polymer-free binder may be added to the aqueous ink.

The production process of conventional fuel cells sometimes includes more than 100 steps and uses tens of machines. According to an embodiment of the present disclosure, a method of making a fuel cell includes using only one AMM to produce a fuel cell, wherein the fuel cell includes an anode, an electrolyte, and a cathode. In a preferred embodiment, the fuel cell comprises at least one barrier layer located, for example, between the electrolyte and the cathode or both. Preferably, at least one barrier layer is also prepared by the same AMM. In a preferred embodiment, the AMM may also produce and assemble the interconnect with the anode, the cathode, the at least one barrier layer, and the electrolyte. These production methods and systems are suitable for use not only in the manufacture of fuel cells, but also in the manufacture of other types of electrochemical devices. The following discussion uses a fuel cell as an example, but any reactor or catalyst is within the scope of the present disclosure.

In various embodiments, a single AMM produces a first fuel cell, wherein the fuel cell comprises an anode, an electrolyte, a cathode, at least one barrier layer, and an interconnect. In various embodiments, a single AMM prepares the second fuel cell. In various embodiments, a single AMM is used to assemble a first fuel cell with a second fuel cell to form a fuel cell stack. In various embodiments, the production of fuel cells using AMM is repeated as many times as necessary. Thus, a fuel cell stack including two or more fuel cells is assembled using the AMM. In some embodiments, the layers of the fuel cell are produced by the AMM being above ambient temperature. For example, the temperature may be higher than 100 ℃, in the range of 100 ℃ to 500 ℃, or in the range of 100 ℃ to 300 ℃. In various embodiments, the fuel cell or fuel cell stack is heated after it is assembled. In some embodiments, the fuel cell or fuel cell stack is heated at a temperature greater than 500 ℃. In a preferred embodiment, the fuel cell or fuel cell stack is heated at a temperature in the range of 500 ℃ to 1500 ℃.

In various embodiments, the AMM comprises a chamber in which fuel cell production is performed. The chamber may be capable of withstanding high temperatures to enable production of fuel cells, wherein the high temperatures are at least 300 ℃, at least 500 ℃, at least 1000 ℃, or at least 1500 ℃. In some cases, the chamber may also enable heating of the fuel cell to be performed in the chamber. A variety of heating methods may be applied, such as laser heating/curing, electromagnetic wave heating, thermal fluid heating, or one or more heating elements in combination with the chamber. The heating element may be a heating surface, a heating coil, or a heating rod, and is coupled to the chamber to heat the contents of the chamber to a desired temperature range. In various embodiments, the chamber of the AMM may also be capable of applying pressure to the interior of the fuel cell. For example, the pressure may be applied by a moving element, such as a moving ram or piston. In various embodiments, the chamber of the AMM is capable of withstanding pressure. The chamber may be pressurized or depressurized by a fluid as desired. The fluid in the chamber may also be changed or replaced as desired.

In a preferred embodiment, EMR is used to heat the fuel cells or fuel cell stack. In other embodiments, an oven cure may be used to heat the fuel cell or fuel cell stack. In other embodiments, the laser beam may be expanded (e.g., by using one or more mirrors) to create a heating zone with a uniform power density. In a preferred embodiment, each layer of the fuel cell can be cured by EMR alone. In a preferred embodiment, a combination of fuel cell layers can be cured with EMR alone, for example, a combination of anode, electrolyte and cathode layers. In some embodiments, the first fuel cell EMR is cured, assembled with the second fuel cell, and then the second fuel cell EMR is cured. In one embodiment, the first fuel cell is assembled with the second fuel cell, and then the first fuel cell and the second fuel cell are cured with EMR alone. In one embodiment, a first fuel cell is assembled with a second fuel cell to form a fuel cell stack, and then the fuel cell stack EMR is cured. A fuel cell stack EMR comprising two or more fuel cells may be cured. The sequence of laser heating/curing and assembly is applicable to all other heating methods.

In a preferred embodiment, the AMM produces each layer of multiple fuel cells simultaneously. In a preferred embodiment, the AMM assembles each layer of the plurality of fuel cells simultaneously. In a preferred embodiment, the heating of each layer or the heating of a combination of layers of a plurality of fuel cells is performed simultaneously. All of the discussion and all of the features herein with respect to a fuel cell or fuel cell stack apply to the production, assembly, and heating of a plurality of fuel cells. In preferred embodiments, the plurality 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.

Treatment method

Disclosed herein are treatment methods that include one or more of the following effects: heating, drying, curing, sintering, annealing, sealing, alloying, evaporating, reconstructing, foaming or sintering. The preferred treatment method is sintering. The treatment method includes exposing the substrate to an electromagnetic radiation (EMR) source. In some embodiments, EMR is exposed to a substrate having a first material. In various embodiments, the EMR has a peak wavelength in the range of 10 to 1500 nm. In various embodiments, the EMR has a value of 0.1J/cm ² Is a minimum energy density of (c). In one embodiment, the EMR has 10 ^-4 -1000 Hz, alternatively 1-1000 Hz, alternatively 10-1000 Hz. In one embodiment, the EMR exposure distance is no greater than 50 mm. In one embodiment, the EMR exposure time is no less than 0.1 ms or 1 ms. In one embodiment, a capacitor voltage of not less than 100V is applied to the EMR. For example, a single pulse of EMR is applied at an exposure distance of about 10 mm and an exposure time of 5-20 ms. For example, multiple pulses of EMR are applied at a pulse frequency of 100 Hz at an exposure distance of about 10 mm and an exposure time of 5-20 ms. In some embodiments, the EMR consists of one exposure. In other embodiments, the EMR includes no more than 10 exposures, or no more than 100 exposures, or no more than 1000 exposures, or no more than 10,000 exposures.

In various embodiments, using pulsed light, metals and ceramics sinter almost instantaneously (for<<10 microns, milliseconds). The sintering temperature may be controlled in the range of 100 to 2000 ℃. The sintering temperature may be adjusted as a function of depth. In one example, the surface temperature is 1000 ℃, and the shallow surface (subsurface) is maintained at 100 ℃, where the shallow surface is 100 microns below the surface. In some embodiments, materials suitable for the treatment process include yttria-stabilized zirconia (YSZ), 8YSZ (8 mol% YSZ powder), yttrium, zirconium, gadolinium oxide doping Ceria (GDC or CGO), samarium oxide doped ceria (SDC), scandium oxide stabilized zirconia (SSZ), lanthanum Strontium Manganite (LSM), strontium lanthanum cobalt ferrite (LSCF), lanthanum Strontium Cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel, niO-YSZ, cu-CGO, cu ₂ O, cuO, cerium, copper, silver, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof. The treatment method may be adapted to any of the electrodes or electrolyte materials previously listed herein.

This treatment method is suitable for use in a method of producing a fuel cell. In a preferred embodiment, the layers (i.e., anode, cathode, electrolyte, seal, catalyst, etc.) in the fuel cell are treated using the methods described herein to heat, cure, sinter, seal, alloy, foam, evaporate, reconstruct, dry or anneal or a combination thereof. In a preferred embodiment, portions of the layers in the fuel cell are treated using the methods described herein to heat, cure, sinter, seal, alloy, foam, evaporate, reconstruct, dry, anneal, or a combination thereof. In a preferred embodiment, the combination of layers of the fuel cell, which may be complete layers or partial layers, is treated using the methods described herein to heat, cure, sinter, seal, alloy, foam, evaporate, reconstruct, dry, anneal, or a combination thereof.

The processing method of the present disclosure is preferably rapid, with processing durations varying from microseconds to milliseconds. The processing duration can be accurately controlled. The treatment methods of the present disclosure can produce fuel cell layers with no or minimal cracking. The treatment method of the present disclosure controls the power density or energy density in the treatment volume of the material to be treated (the volume of the object to be treated). The process volume can be accurately controlled. In one embodiment, the treatment methods of the present disclosure provide the same energy density or different energy densities in the treatment volume. In one embodiment, the treatment methods of the present disclosure provide the same treatment duration or different treatment durations in the treatment volume. In one embodiment, the treatment methods of the present disclosure provide simultaneous treatment for one or more treatment volumes. In one embodiment, the treatment methods of the present disclosure provide simultaneous treatment for one or more fuel cell layers or portions or combinations of layers. In one embodiment, the process volume is changed by changing the process depth.

In one embodiment, a first portion of the treatment volume is treated by electromagnetic radiation having a first wavelength; a second portion of the treatment volume is treated by electromagnetic radiation having a second wavelength. In some cases, the first wavelength is the same as the second wavelength. In some cases, the first wavelength is different from the second wavelength. In one embodiment, the first portion of the treatment volume has a different energy density than the second portion of the treatment volume. In one embodiment, the first portion of the processing volume has a different processing duration than the second portion of the processing volume.

In one embodiment, the EMR has a broad emission spectrum, thereby achieving the desired effect for a wide range of materials with different absorption characteristics. In this disclosure, absorption of electromagnetic radiation (EMR) refers to a process in which electrons of a substance, such as an atom, absorb photon energy. Thus, electromagnetic energy is converted into the internal energy of the absorber, e.g., thermal energy. For example, the EMR spectrum extends from the far Ultraviolet (UV) range to the near Infrared (IR) range with peak pulse power at 220 nm wavelengths. The power of this EMR is about megawatts. Such EMR sources perform tasks such as breaking chemical bonds, sintering, ablating, or sterilizing.

In one embodiment, the EMR has an energy density of not less than 0.1, 1 or 10 joules/cm ² . In one embodiment, the power output of the EMR is no less than 1 watt (W), 10W, 100W, 1000W. The EMR delivers no less than 1W, 10W, 100W, 1000W power to the substrate. In one embodiment, such EMR exposure heats the material in the substrate. In one embodiment, the EMR has a range or spectrum of different wavelengths. In various embodiments, the treated substrate is at least a portion of an anode, cathode, electrolyte, catalyst, barrier, or interconnect of a fuel cell.

In one embodiment, the peak wavelength of EMR is between 50 and 550 nm or between 100 and 300 nm. In one embodiment, at least a portion of the substrate absorbs no less than 30% or no less than 50% of at least one frequency of EMR between 10 and 1500 nm. In one embodiment, at least a portion of the substrate absorbs no less than 30% or no less than 50% of at least one frequency between 50 and 550 nm. In one embodiment, at least a portion of the substrate absorbs no less than 30% or no less than 50% of at least one frequency between 100 and 300 nm.

Sintering is a process by which solid matter of a material is compacted and formed by heat or pressure without melting it to the point of liquefaction. In the present disclosure, the EMR-exposed substrate is sintered but not melted. In preferred embodiments, the EMR includes one or more of UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, microwaves. In one embodiment, the substrate is exposed to EMR for not less than 1 microsecond, not less than 1 millisecond. In one embodiment, the substrate is exposed to EMR for less than 1 second at a time or less than 10 seconds at a time. In one embodiment, the substrate is exposed to EMR for less than 1 second or less than 10 seconds. In one embodiment, the substrate is repeatedly exposed to EMR, e.g., greater than 1, greater than 3, greater than 10 times. In one embodiment, the substrate is less than 50 cm, less than 10 cm, less than 1 cm, or less than 1 mm from the EMR source.

In some embodiments, the second material is added to or placed on the first material after EMR exposure. In many cases, the second material is the same as the first material. The second material may be exposed to EMR. In some cases, a third material may be added. The third material is exposed to EMR.

In some embodiments, the first material comprises YSZ, 8YSZ, yttrium, zirconium, GDC, SDC, LSM, LSCF, LSC, nickel, niO, or cerium, or a combination thereof. The second material may comprise graphite. In some embodiments, the electrolyte, anode, or cathode comprises a second material. In some cases, the volume fraction of the second material in the electrolyte, anode, or cathode is less than 20%, 10%, 3%, or 1%. The second material has an absorptivity of greater than 30% or greater than 50% for at least one frequency (e.g., between 10 and 1500 nm, or between 100 and 300 nm, or between 50 and 550 nm).

In various embodiments, a parameter or combination of parameters may be controlled, where the parameters include the distance between the EMR source and the substrate, the energy density of the EMR, the EMR spectrum, the EMR voltage, the exposure time, the pulse frequency, and the number of EMR exposures. Preferably, these parameters are controlled to minimize the formation of cracks in the substrate.

In one embodiment, EMR energy is delivered to not less than 1 mm ² Or not less than 1 cm ² Or not less than 10 cm ² Or not less than 100 cm ² Is a surface area of the substrate. In some cases, at least a portion of the adjacent material is at least partially heated by heat conduction from the first material during EMR exposure of the first material. In various embodiments, the fuel cell (e.g., anode, cathode, electrolyte) layers are thin. Preferably, they are no greater than 30 microns, no greater than 10 microns, or no greater than 1 micron.

In some embodiments, the first material of the substrate is in the form of a powder, sol gel, colloidal suspension, hybrid solution, or sintered material. In various embodiments, the second material may be added by vapor deposition. In a preferred embodiment, the second material coats the first material. In a preferred embodiment, the second material reacts with light (e.g., focused light), such as by light from a laser, and sinters or anneals with the first material.

Advantages and advantages

The preferred treatment method of the present disclosure enables the rapid production of fuel cells by eliminating conventional, costly, time consuming, expensive sintering processes and replacing them with rapid, in situ processes that allow for continuous production of fuel cell layers in a single machine, if desired. The method also shortens the sintering time from hours to days to seconds or milliseconds or even microseconds.

In various embodiments, this treatment method is used in combination with production techniques such as screen printing, cast molding, spraying, sputtering, physical vapor deposition, and additive manufacturing.

This preferred treatment method enables the adjustment and control of heating by adjusting EMR characteristics (such as wavelength, energy density, pulse frequency, and exposure time) in combination with controlling the thickness of the base layer and the heat conduction to adjacent layers such that each layer sinters, anneals, or cures at each desired target temperature. This approach makes the energy application more uniform, reducing or eliminating cracking, which improves electrolyte performance. Substrates treated with this preferred method also have lower thermal stresses due to more uniform heating.

Particle size control

Without wishing to be bound by any theory, we have unexpectedly found that if the particle size distribution of the particles in the material is controlled to meet certain criteria, the sintering process may require less energy consumption and less time than conventionally required. In some cases, such a particle size distribution comprises 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 1.5 to 100. In some cases, this 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. In some cases, such a particle size distribution includes D50, wherein 50% of the particles have a diameter no greater than D50, wherein D50 is no greater than 100 nm. The sintering process uses electromagnetic radiation (EMR), or plasma, or furnace, or hot fluid, or heating elements, or a combination thereof. Preferably, the sintering process uses electromagnetic radiation (EMR). For example, without the use of the methods as disclosed herein, the EMR source is only sufficient to sinter a material having a power capacity P. Using the methods as disclosed herein, materials are sintered with EMR sources having much lower power capacities, 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.

Herein, a method of sintering a material is disclosed, 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 1.5 to 100; depositing the dispersion on a substrate to form a layer; and treating the layer to cause sintering of at least a portion of the particles.

In some embodiments, the particle size distribution is a number average distribution determined by dynamic light scattering. Dynamic Light Scattering (DLS) is a technique that can be used to determine the particle size distribution spectrum of small particles in a dispersion or suspension. In the context of DLS, transient fluctuations are typically analyzed by intensity or photon autocorrelation functions (also known as photon correlation spectroscopy or quasi-elastic light scattering). In time domain analysis, the autocorrelation function (ACF) generally decays from zero delay time, and the faster dynamics due to smaller particles will result in faster decorrelation of the scattering intensity trace. Intensity ACF has been shown to be a fourier transform of the power spectrum and thus DLS measurements can be made equally well in the spectral domain.

In one embodiment, the particle size distribution is determined by Transmission Electron Microscopy (TEM). TEM is a microscopic technique in which an electron beam is transmitted through a sample to form an image. In this case, the sample is most typically a suspension on a grid (grid). As the beam is transported through the sample, an image is formed due to the interaction of the electrons with the sample. The image is then magnified and focused onto an imaging device, such as a phosphor screen or a sensor, such as a scintillator attached to a charge-coupled device.

Herein, a method of sintering a material is disclosed, 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 sintering of at least a portion of the particles. In various embodiments, 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. In one embodiment, the thickness of the layer is 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.

In some embodiments, depositionIncluding material jetting, binder jetting, ink jet printing, aerosol jetting or aerosol jet printing, slot photopolymerization, powder layer fusion, material extrusion, directional energy deposition, sheet lamination, ultrasonic ink jet printing, or combinations thereof. In some embodiments, the liquid comprises water and at least one organic solvent having a boiling point lower than that of water and being miscible with water. In some embodiments, the liquid includes water, a surfactant, a dispersant, and does not include a polymeric binder. In some embodiments, the liquid comprises one or more organic solvents and does not include water. In some embodiments, the particles comprise Cu, cuO, cu ₂ O、Ag、Ag ₂ O、Au、Au ₂ O、Au ₂ O ₃ Titanium, yttria Stabilized Zirconia (YSZ), 8YSZ (8 mol% YSZ powder), yttrium, zirconium, gadolinium oxide doped ceria (GDC or CGO), samarium oxide doped ceria (SDC), scandium oxide stabilized zirconia (SSZ), lanthanum Strontium Manganite (LSM), lanthanum cobalt ferrite (LSCF), lanthanum Strontium Cobaltite (LSC), lanthanum strontium gallium magnesium oxide (LSGM), nickel (Ni), niO-YSZ, cu-CGO, cerium, crofer, steel, lanthanum chromite, doped lanthanum chromite, ferritic steel, stainless steel, or combinations thereof. The particles may comprise any of the materials listed herein previously for the electrodes or electrolytes.

In some embodiments, wherein the particles have a bimodal particle size distribution such that the average particle size in the first mode is at least 5 times the average particle size in the second mode. In some embodiments, D10 is in the range of 5 nm to 50 nm, or 5 nm to 100 nm, or 5 nm to 200 nm. In some embodiments, D90 is in the range of 50 nm to 500 nm, or 50 nm to 1000 nm. In some embodiments, D90/D10 is in the range of 2 to 100, or 4 to 100, or 2 to 20, or 2 to 10, or 4 to 20, or 4 to 10.

In some embodiments, the method includes drying the dispersion after deposition. In some embodiments, drying includes heating the dispersion prior to deposition, heating the substrate in contact with the dispersion, or a combination thereof. Drying may occur for a period of time 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 ℃ to 100 ℃, or 50 ℃ to 90 ℃, or 60 ℃ to 80 ℃, or about 70 ℃.

In some embodiments, the treatment includes the use of electromagnetic radiation (EMR), or an oven, or a plasma, or a thermal fluid, or a heating element, or a combination thereof. In some embodiments, the EMR includes UV light, near ultraviolet light, near infrared light, visible light, laser light, electron beam, or microwaves, or a combination thereof. In one embodiment, the EMR consists of one exposure. In other embodiments, the EMR exposure frequency is 10 ^-4 -1000 Hz, alternatively 1-1000 Hz, alternatively 10-1000 Hz. In one embodiment, the EMR exposure distance is no greater than 50 mm. In one embodiment, the EMR exposure time is no less than 0.1 ms or 1 ms. In one embodiment, a capacitor voltage of not less than 100V is applied to the EMR.

Examples

The following examples are provided as part of the disclosure of various embodiments of the invention. As such, none of the information provided below is to be considered as limiting the scope of the present invention.

Example 1. An EC reactor stack was prepared.

Example 1 illustrates a preferred method of preparing an EC reactor stack, e.g., a fuel cell stack. The method uses AMM type 0012323 from Cerarop and EMR type 092309423 from Xenon Corp. The interconnect substrate is lowered to begin printing.

As a first step, the anode layer was prepared by AMM. This layer was deposited by AMM as slurry a having the composition shown in the table below. The layer was dried by applying heat via an infrared lamp. The anode layer was sintered by irradiating it for 1 second with an electromagnetic pulse from a xenon pulse tube.

An electrolyte layer was formed on top of the anode layer by AMM deposition of slurry B having the composition shown in the table below. The layer was dried by applying heat via an infrared lamp. The electrolyte layer was sintered by irradiating it with electromagnetic pulses from a xenon pulse tube for 60 seconds.

Then, a cathode layer was formed on top of the electrolyte layer by AMM deposition of a paste C having the composition shown in the table below. The layer was dried by applying heat via an infrared lamp. The cathode layer was sintered by irradiating it for 1/2 second with an electromagnetic pulse from a xenon pulse tube.

An interconnect layer was formed on top of the cathode layer by AMM deposition of paste D, which has the composition shown in the table below. The layer was dried by applying heat via an infrared lamp. The interconnect layer was sintered by irradiating it for 30 seconds with an electromagnetic pulse from a xenon pulse tube.

These steps are then repeated 60 times with an anode layer formed on top of the interconnect. The result is a fuel cell stack having 61 fuel cells.

EXAMPLE 2 LSCF in ethanol

200 ml ethanol was mixed with 30 grams of LSCF powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper layer dispersion was extracted and deposited on the substrate using a 3D printer and an LSCF layer was formed. The LSCF layer was irradiated using a xenon lamp (10 kW) at 400V voltage and 10 Hz pulse frequency for a total exposure time of 1,000 ms.

EXAMPLE 3 CGO in ethanol

200 ml ethanol was mixed with 30 grams of CGO powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper layer dispersion is extracted and deposited on the substrate using a 3D printer and a CGO layer is formed. The CGO layer was irradiated using a xenon lamp (10 kW) at 400V voltage and 10 Hz pulse frequency for a total exposure time of 8,000 ms.

EXAMPLE 4 CGO in Water

200 ml deionized water was mixed with 30 grams of CGO powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper layer dispersion is extracted and deposited on the substrate using a 3D printer and a CGO layer is formed. The CGO layer was irradiated using a xenon lamp (10 kW) at 400V voltage and 10 Hz pulse frequency for a total exposure time of 8,000 ms.

Example 5 NiO in Water

200 ml deionized water was mixed with 30 grams of NiO powder in a beaker. The mixture was centrifuged and an upper dispersion and a lower dispersion were obtained. The upper dispersion was extracted and deposited on the substrate using a 3D printer and a NiO layer was formed. The NiO layer was irradiated using a xenon lamp (10 kW) at 400V voltage and 10 Hz pulse frequency for a total exposure time of 15,000 ms.

EXAMPLE 6 sintering results

Fig. 17 is a scanning electron microscope image (side view). Fig. 17 shows an electrolyte (YSZ) 1701 printed and sintered on an electrode (NiO-YSZ) 1702. The scanning electron microscope image shows a side view of the sintered configuration, which demonstrates the gas-tight contact between the electrolyte and the electrode, the complete densification of the electrolyte and the microstructure of the sintered and porous electrode.

Example 7 Fuel cell Stack Structure

The 48-volt fuel cell stack has 69 cells, about 1000 watts of power output. The fuel cells in the stack have dimensions of about 4 cm ×4 cm (length×width) and about 7 cm height. The 48-volt fuel cell stack has 69 cells with a power output of about 5000 watts. The fuel cells in the stack had dimensions of about 8.5 cm x 8.5 cm (length x width) and about 7 cm height.

Example 8 channeled electrode/fluid dispersion Assembly

Fig. 18 schematically shows an example of half-cells in an EC reactor. As shown in fig. 18, half cell 1700 includes interconnect 1801. Interconnect 1801 includes doped lanthanum chromite. The half cell 1800 includes an anode segment 1802 printed onto an interconnect 1801. The anode segment consisted of NiO-YSZ. The anode segment 1802 was sintered using EMR (see example 1). Half cell 1800 includes a filler material deposited between anode segments 1802. The filler material is polymethyl methacrylate (PMMA). Half cell 1800 includes a protective layer 1804 printed onto a filler material 1803 comprised of YSZ. Other anode material 1806 is printed to cover the anode segments 1802 and the protective layers 1804, followed by sintering using EMR. Other anode materials consist of NiO-YSZ. The electrolyte 1805 is printed onto the other anode material 1806 and sintered using EMR. Electrolyte 1805 is YSZ. A barrier layer (not shown) composed of CGO was further printed onto the electrolyte and sintered using EMR. A cathode layer (not shown) composed of LSCF was printed onto the CGO barrier layer and sintered. A cathode segment (not shown) consisting of LSCF is printed onto the layer and sintered. These segments form valleys and filler PMMA is deposited to fill the valleys (not shown). A protective layer composed of YSZ was printed onto the filler (not shown). The doped lanthanum chromite is printed to cover the protective layer and cathode segments and then sintered to form another interconnect (not shown). The charge is removed by furnace heating and channeled electrodes are created or a fluid dispersion assembly (not shown) is formed between the electrolyte and the interconnect.

It is to be understood that this disclosure describes exemplary embodiments for implementing different features, structures and functions of the present invention. Exemplary embodiments of components, arrangements and configurations are described to simplify the present disclosure; however, these exemplary embodiments are provided by way of example only and are not intended to limit the scope of the invention. Embodiments as provided herein may be combined unless otherwise indicated. Such combinations do not depart from the scope of the present disclosure.

In addition, certain terms are used throughout the description and claims to refer to particular components or steps. As one of ordinary skill in the art will appreciate, various entities may refer to the same component or method step by different names, and as such, naming rules for the elements described herein are not intended to limit the scope of the present invention. Furthermore, the terms and naming convention used herein are not intended to distinguish between components, features, and/or steps that differ in name, but not function.

While the disclosure is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and the description. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the disclosure to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present disclosure.

Claims

1. A method of producing hydrogen, the method comprising: providing a device comprising a first electrode and a second electrode, each in contact with and separated by an electrolyte, introducing a first stream comprising fuel into the first electrode of the device, introducing a second stream comprising water and hydrogen into the second electrode of the device, reducing the water in the second stream to hydrogen, and extracting hydrogen from the device, wherein both the first electrode and the second electrode comprise metallic phase nickel and are simultaneously exposed to a reducing environment during the entire operating time of the device; and wherein the electrolyte is hybrid conductive, and wherein the device does not receive electricity or does not generate electricity.

2. The method of claim 1, wherein the first stream is not contacted with the hydrogen.

3. The method of claim 1, wherein the first and second streams are separated in the device by an electrolyte.

4. The method of claim 1, wherein the electrolyte is oxygen ion conductive and is solid.

5. The method of claim 1, wherein the electrolyte comprises doped ceria, or wherein the electrolyte comprises lanthanum chromite or a conductive metal, or a combination thereof, and a material selected from the group consisting of: doped ceria, YSZ, LSGM, SSZ, and combinations thereof.

6. The method of claim 5, wherein the lanthanum chromite comprises undoped lanthanum chromite, strontium doped lanthanum chromite, iron doped lanthanum chromite, lanthanum calcium chromite, or a combination thereof. And wherein the conductive metal comprises Ni, cu, ag, au or a combination thereof.

7. The method of claim 1, wherein the device does not include an interconnect.

8. The method of claim 1, wherein the device is tubular.

9. The method of claim 1, wherein the first stream further comprises water or carbon dioxide.

10. The method of claim 1, wherein the device is planar.

11. The method of claim 1, wherein the electrode comprises a fluid channel or a fluid dispersion assembly.

12. The method of claim 1, wherein the device is operated at a temperature of not less than 500 ℃.

13. The method of claim 1, wherein the first electrode or the second electrode comprises Ni or NiO and a material selected from the group consisting of: YSZ, CGO, SDC, SSZ, LSGM, and combinations thereof.

14. The method of claim 1, wherein the first electrode comprises a catalyst.

15. The method of claim 1, wherein the fuel comprises a hydrocarbon or hydrogen or carbon monoxide or a combination thereof.