Method and system for commercially manufacturing tubular solid oxide fuel cells

Abstract

The present invention relates to a method and system for producing tubular ceramic green bodies that can be converted into tubular solid oxide fuel cells.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 498,118, filed on April 25, 2023, the entire disclosure of which is hereby incorporated by reference in its entirety for all purposes.

[0002] The present invention relates to a method and system for manufacturing a tubular ceramic green body that can be converted into a tubular solid oxide fuel cell.

Background Art

[0003] Tubular ceramic structures are known to be used as heat exchangers, recuperators, catalysts that encounter corrosive liquids or gases, components of fuel cells, particularly solid oxide fuel cells (SOFCs), and in various other applications. In recent years, SOFCs have attracted attention as a means of portable and distributed power generation for green energy production and for supplying electricity in remote or residential applications. Among various designs, micro or macro tubular SOFCs offer many advantages.

[0004] Tubular ceramic structures for SOFCs can be manufactured using the method described in U.S. Patent No. 9,542,548, which can manufacture tubular ceramic structures over a wide range of wall thicknesses, i.e., from very thin to very thick, without requiring meticulous attention and control of drying conditions, can easily change or modify the composition of the tubular product for defined portions of the tubular product, and does not require the use of a tubular substrate defined to be a permanent component of the product. The technology described therein is effective, but commercial SOFC unit manufacturing requires thousands of tubular SOFCs when using bundles of micro or macro tubular SOFCs.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, there is a need to improve the efficiency of fabricating tubular ceramic green bodies for use in tubular solid oxide fuel cells, as well as to develop improved methods for cutting the resulting tubular ceramic green bodies without damaging their structure. [Means for solving the problem]

[0006] In light of the above, the present invention provides a method and system that can improve the production efficiency of tubular ceramic green bodies, which are precursors of tubular SOFCs. The method and system of the present invention are particularly useful for the commercial production of such tubular SOFCs because the method can be automated. This method may include inspection of tubular ceramic greens during their manufacture, so that defective tubular ceramic greens can be removed and reused before firing.

[0007] More specifically, the method of the present invention generally involves forming a tubular ceramic green body by coating different ceramic formation layers around a spindle. Furthermore, the ceramic formation layers may have completely different compositions, for example, an anode formation layer versus an electrolyte formation layer, or their compositions may be slightly different. For example, during the formation of the anode formation layer, the elemental composition of the anode formation layer may change depending on the requirements of specific characteristics or structures. Defects and dimensional issues can be inspected at various points during the process of forming the tubular ceramic green body, and if the subsequently added ceramic cleft layer cannot repair the defects and / or dimensional issues, the defective tubular ceramic green body can be recycled. Furthermore, since the dimensions of this tubular ceramic green body can be measured in real time, the layer thickness can be carefully controlled, and it is possible to indicate if additional layers are needed to meet the specifications.

[0008] Finally, the present invention provides a method for cutting such tubular ceramic green bodies without damaging the underlying structure, so that a clean cut is achieved.

[0009] These and other features of the present invention are described more fully herein.

[0010] Accordingly, the present invention provides a method for manufacturing a tubular ceramic green body, the method comprising the steps of providing a cartridge comprising a plurality of mandrel spindle assemblies, wherein the lengths of the plurality of mandrel spindle assemblies are parallel to each other and lie in the same horizontal plane along the cartridge, the cartridge is fitted to rotate each of the plurality of mandrel spindle assemblies, each mandrel spindle assembly comprises a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a disappearing tube, or a coating on the spindle component, the outer surface thereof corresponding to the inner surface of the tubular ceramic green body to be manufactured, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact, The steps include rotating multiple mandrel spindle assemblies and applying an anode-forming layer to each of the mandrels of each of the multiple rotating mandrel spindle assemblies of the cartridge to form multiple anode-forming green bodies around each spindle, A step of inspecting each of the multiple anode-forming green bodies for defects, The process involves rotating multiple anode-forming green bodies and applying an interface-forming layer to each of the multiple rotating anode-forming green bodies of the cartridge to form multiple multilayer green bodies around each spindle, Steps include inspecting each of the multiple multilayered green bodies for defects, The steps include rotating multiple multilayer green bodies and applying an electrolyte-forming layer to each of the multiple rotating multilayer green bodies of the cartridge to form multiple tubular ceramic green bodies around each spindle, A step of inspecting each of the multiple tubular ceramic green bodies for defects, The process includes the step of removing a spindle containing a tubular ceramic green body that has been identified as having defects during inspection, before firing the tubular ceramic green body.

[0011] Furthermore, the present invention provides a system for manufacturing tubular ceramic green bodies. This system A cartridge comprising multiple mandrel spindle assemblies, wherein the lengths of the multiple mandrel spindle assemblies are parallel to each other and coplanar along the cartridge, the cartridge is fitted to rotate each of the multiple mandrel spindle assemblies, each mandrel spindle assembly comprising a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a disappearing tube, or a coating on the spindle component, the outer surface of which corresponds to the inner surface of a manufactured tubular ceramic green body, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact with the cartridge, A first printer station, wherein an anode-forming layer is applied to each of the mandrels of a plurality of rotating mandrel spindle assemblies of a cartridge, forming a plurality of anode-forming green bodies around each mandrel. A second printer station, wherein an interface forming layer is applied to each of the anode forming green bodies of a plurality of rotating anode forming green bodies of a cartridge, forming a plurality of multilayer green bodies around each mandrel, A third printer station, wherein an electrolyte-forming layer is applied to each of the multiple rotating multilayer green bodies of the cartridge to form a tubular ceramic green body, An inspection station in which the anode formation layer, interface formation layer, and electrolyte formation layer are inspected for defects after their formation, and the identity of a cartridge mandrel spindle assembly having any defects is recorded. The system includes a controller that automates the movement of cartridges from the first printer station to the inspection station, to the second printer station and the inspection station, and to the third printer station and the inspection station.

[0012] In another aspect, the present invention provides a method for forming multiple tubular ceramic green bodies, for example, around a single spindle. This method, A step of providing a cartridge comprising: multiple mandrel spindle assemblies, wherein the lengths of the multiple mandrel spindle assemblies are parallel to each other and lie in the same horizontal plane along the cartridge, the cartridge is fitted to rotate each of the multiple mandrel spindle assemblies, each mandrel spindle assembly comprises a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a vanishing tube, or a coating on the spindle component, the outer surface of which corresponds to the inner surface of a tubular ceramic green body, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact; and a tubular ceramic green body around each mandrel spindle assembly; The process includes the step of laser cutting a tubular ceramic green body into a plurality of smaller tubular ceramic green bodies along each mandrel spindle assembly.

[0013] The above and other features and advantages of the present invention will be more fully understood from the following drawings, description, examples and claims.

[0014] The drawings described below are for illustrative purposes only. Like reference numerals generally refer to like parts. The drawings are not necessarily to scale and generally focus on explaining the principles of the present invention. The drawings do not in any way limit the scope of the present invention.

Brief Description of the Drawings

[0015] [Figure 1] A perspective view of one embodiment of the present invention showing a mandrel spindle assembly with a partial anode forming layer applied. [Figure 2] A perspective view of one embodiment of the present invention showing a cartridge including seven mandrel spindle assemblies. [Figure 3A] A cross-sectional view of a mandrel spindle assembly with an anode forming layer applied, where the outer diameter (and thickness) is being measured using an outer diameter measuring device. [Figure 3B] A cross-sectional view of a mandrel spindle assembly with an anode forming layer applied, where the outer diameter (and thickness) is being measured using an outer diameter measuring device. [Figure 3C] A cross-sectional view of a mandrel spindle assembly with an anode forming layer applied, where the outer diameter (and thickness) is being measured using an outer diameter measuring device. [Figure 4] A top view of one embodiment of the system of the present invention showing a storage station, a printer station, an inspection station including a real-time outer diameter measuring device, a laser cutting station including a laser, and a robotic tray capable of moving a cartridge between each of the stations. [Figure 5]A top view of one embodiment of the system of the present invention, showing a storage station, three printer stations, three inspection stations, a laser cutting station, and a conveyor belt that can move cartridges between each station. [Modes for carrying out the invention]

[0016] Currently, systems and methods exist for the commercial production of tubular ceramic green bodies that can be converted into tubular SOFCs, such as micro and macro tubular SOFCs, for fuel cell bundles. Generally, the system and method include a plurality of printer stations for coating ceramic formation layers and one or more inspection stations. Furthermore, the system and method may include a laser cutting station that includes a laser. By including inspection of tubular ceramic green bodies while they are being prepared to identify defects and dimensional issues, it becomes possible to move such defective tubes further during manufacturing, for example, by firing them to prepare them for fuel cell units, which would then simply result in them being rejected in the final product. The method and system may, in particular, include measuring the outer diameter of the ceramic formation layer in real time as the ceramic formation layer is being applied to ensure uniformity between tubular ceramic green bodies.

[0017] The system and method may include a storage station for maintaining a plurality of cartridges for use in the method of the present invention. Furthermore, this storage station can maintain cartridges that are ready for the application of the ceramic cambium and / or cartridges that have completed tubular ceramic green bodies. Furthermore, there are two or more storage stations, each equipped with appropriate active environmental control, for example, for temperature and humidity control, so that cartridges with finished products can be stored in a dedicated storage station and cartridges ready for manufacturing can be stored in another storage station.

[0018] The system of the present invention may include a controller for computer-related operations of the method, for example, for the use of robotic equipment for moving cartridges to different stations of the system. Furthermore, this robotic device can take various forms, and for simplicity, in this specification, we will use the term "robot tray" to refer to such a robotic device, which may include a robotic arm and means of transport such as a wheeled robotic device, or a device on a track or rail that can move between different components of the system and stations to place and remove cartridges at each station. Furthermore, the system and method may include using a laser to cut a tubular ceramic green body to a predetermined length, so that the ends of the tube are uniformly cut and have a vertical structure, thereby avoiding some of the difficulties of other cutting methods and systems. Furthermore, lasers can be used to cut holes in tubular ceramic green bodies and / or to form tapered ends for manifolds and current collection. Other shapes and openings can be formed in a similar manner, depending on the specific application and requirements.

[0019] By automating the preparation of tubular ceramic green bodies, the system of the present invention can be installed in a cleanroom, minimizing human intervention and errors in the process, and this can be a nearly continuous operation. For example, an intermediate room may exist for the exchange of storage stations inside and outside the cleanroom, for the movement of finished cartridges from the cleanroom and the introduction of blank cartridges (mandrel spindle assemblies). Furthermore, the cleanroom, intermediate chamber, and one or more stations may have associated environmental control features so as to allow for appropriate control of temperature and humidity for the formation and storage of the tubular ceramic green bodies of the present invention.

[0020] To facilitate understanding of the present invention, several terms and phrases are defined below.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this invention pertains.

[0022] Throughout the present invention, where a composition is described as having, containing, or containing a particular component, or where a method is described as having, containing, or containing a particular process, it is intended that the compositions of the present invention also consist essentially of or comprise the listed components, and the methods of the present invention also consist essentially of or comprise the listed process.

[0023] In the present invention, it is said that an element or component is included in the enumerated list of elements or components, and / or selected from the enumerated list of elements or components, where the element or component may be any one of the enumerated elements or components, or the element or component is selected from a group consisting of two or more of the enumerated elements or components.

[0024] Furthermore, elements and / or features of the compositions, apparatus, or methods described herein can be combined in various ways, whether expressly or implicitly, without departing from the spirit and scope of the invention. For example, when referring to a particular structure, that structure can be used in various embodiments of the apparatus of the present invention and / or in the methods of the present invention, unless otherwise specifically understood from the context. In other words, while embodiments have been described and illustrated in a manner that enables clear and concise application descriptions and illustrations within the present invention, embodiments can be combined and separated in various ways without departing from the present invention. For example, all features described and illustrated herein are applicable to all embodiments of the present invention described and illustrated herein.

[0025] The expression "at least one of ~" is understood to include each of the enumerated items after the expression, and various combinations of two or more of the enumerated items, unless otherwise understood from the context and usage. Expressions like "and / or" relating to three or more enumerated items should be understood to have the same meaning unless otherwise specified in the context.

[0026] The use of the terms "include," "includes," "including," "have," "has," "having," "contain," "contains," or "containing," including their grammatical equivalents, is generally understood to be unrestricted and non-exclusive, and does not exclude any further elements or steps not listed, for example, unless specifically stated or understood from the context.

[0027] In this specification, the use of singular nouns, such as "a," "an," and "the," includes the plural nouns (and vice versa) unless otherwise specified.

[0028] When the term "approximately" is used before a quantitative value, the present invention also includes the specific quantitative value itself unless otherwise specified. As used herein, the term “approximately” means a variation of ±10%, ±5%, ±3%, ±2%, or ±1% from the nominal value, unless otherwise indicated or inferred.

[0029] Where percentages are provided in relation to the amount of components or materials in a structure or composition, those percentages are based on weight unless otherwise specified or understood from the context.

[0030] For example, when a molecular weight other than the absolute value of a polymer is provided, that molecular weight is understood to be the average molecular weight unless otherwise specified or understood from the context.

[0031] As long as the present invention remains operational, the order of the steps or the order in which certain operations are performed is not important. Furthermore, two or more steps or actions may be performed simultaneously.

[0032] In various parts of this specification, numerical values ​​are disclosed in groups or ranges. The description is specifically intended to include every possible individual partial combination of members of such groups and ranges, and any combination of various endpoints of such groups or ranges. For example, integers in the range of 0 to 40 are intended to individually disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40, and integers in the range of 1 to 20 are intended to individually disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

[0033] Any examples or illustrative language used herein, such as “such as” or “including,” are intended solely to better illustrate the invention and, unless otherwise claimed, do not limit the scope of the invention. Nothing in this specification should be construed as indicating an element not claimed to be essential for the implementation of the invention.

[0034] Terms and expressions indicating spatial orientation or elevation, such as “upper,” “lower,” “top,” “bottom,” “horizontal,” and “vertical,” are understood herein to have no structural, functional, or operational importance and merely reflect any selected orientation of various views of the apparatus, devices, components, and / or features of the present invention shown in some of the accompanying drawings, unless their use in the context indicates otherwise.

[0035] Generally, the term "ceramic formation layer" refers to any of the "formation layers" described herein, such as an anode formation layer, interface formation layer, electrolyte formation layer, active catalyst formation layer, and inert formation layer. Furthermore, the ceramic composition of this ceramic-forming layer may include a "cermet" in which the ceramic is mixed with reducing metal oxides such as nickel oxide, copper oxide, iron oxide, and / or other transition metal oxides. Furthermore, precious metals can be incorporated into this ceramic-forming layer. After a tubular ceramic green body is formed and fired, the resulting body can be exposed to hydrogen at a predetermined temperature necessary to reduce the incorporated metal oxide phase, thereby generating a "cermet." Furthermore, as used herein, “ceramic composition” may include these components.

[0036] In these terms, “formation layer” refers to a rotating mandrel or a previously coated layer, in particular a slurry of a ceramic composition coated with a certain amount of solvent that remains bonded to the ceramic while the additional layer is being coated. In some embodiments, only the solvent can be printed or sprayed onto an already formed ceramic cleft or green layer.

[0037] Generally, the layers are coated in the following order: first the anode layer, followed by the interface layer, and finally the electrolyte layer. However, this basic structure can be altered by including intermittent inert and active catalyst layers. In other words, an inert layer or an active catalyst layer is the first layer, followed by other such layers or anode layers. The anode layer may include an inert layer and an active catalyst layer scattered therein, and these may be similar for the interfacial layer, including the space between the interfacial layer and the electrolyte layer. Furthermore, the anode-forming layer and interface-forming layer may include layers with different elemental compositions, for example, layers having different proportions and / or different ceramics, metal oxides, and precious metals than the previously coated layer. In certain embodiments, the anode layer and its components do not require an interfacial layer between the electrolyte layers. Furthermore, the present invention includes a tubular inert structure.

[0038] The “layer” described herein may be thinner in the range of approximately 2 microns to approximately 5 microns, or in the range of approximately 50 microns to approximately 800 microns, or 100 microns to approximately 500 microns. Perfect tubular ceramic green bodies range from approximately 150 microns to approximately 1200 microns, for example, approximately 200 microns to approximately 1100 microns, or approximately 500 microns to approximately 1000 microns, or approximately 750 microns to approximately 900 microns. Naturally, layered and complete tubular ceramic bodies can be made thinner or thicker depending on the specific application and design of the tubular structure.

[0039] As described herein, in one embodiment, the present invention provides a system for manufacturing tubular ceramic green bodies. Generally, the system includes a cartridge containing multiple mandrel spindle assemblies, the lengths of which are parallel to each other and coplanar along the cartridge. Furthermore, this cartridge is fitted or configured to rotate each of the multiple mandrel spindle assemblies at the same speed. Each mandrel-spindle assembly comprises a mandrel component and a spindle component. Furthermore, this mandrel component is a heat-shrinkable tube, a disappearing tube, or a coating on a spindle component, the outer surface of which corresponds to the inner surface of the manufactured tubular ceramic green body, the inner surface of which defines the bore, and the spindle component is in close but removable contact with it.

[0040] Figure 1 shows one embodiment of a mandrel spindle assembly 10 including an anode formation layer. The spindle component 12 has a heat-shrinkable tube, a disappearing tube, or a coating 14 thereon. These heat-shrinkable tubes, disappearing tubes, or coatings 14 allow the formed tubular ceramic green body to be removed from the spindle, maintaining and preventing damage to the bore through the tubular ceramic green body. Figure 1 also shows the partial anode-forming layer 16 surrounding the mandrel component 14.

[0041] Figure 2 shows an embodiment of the cartridge 20 of the present invention having seven mandrel spindle assemblies 22. As can be seen from the figure, the lengths of the multiple mandrel spindle assemblies 22 are parallel to each other and lie in the same plane along the cartridge 20. The cartridge 20 then includes a frame that generally has a first side 24 and a second side 26 along with stabilizer bars 28, 30 across two sides to maintain the parallelism of the mandrel spindle assemblies 22 and to fix the cartridge 20 rectangularly in place within two sides. The spindle (mandrel spindle assembly 22) is fixed to rotate as the ceramic formation layer is applied and is laser-cuttable, but it can be independently and detachably fixed within the cartridge 20. The cartridge 20 also includes a rotating mechanism 31 for rotating the mandrel spindle assembly 22, and this rotation can be at the same speed so that the ceramic formation layer can be applied uniformly throughout the mandrel spindle assembly 22. However, the rotation mechanism 31 can be adapted to rotate each spindle independently at different speeds as needed.

[0042] More specifically, one or more rotating mechanisms 31 can come into direct or indirect contact with the spindle on the first side of the frame. The rotation mechanism can rotate each spindle individually, or it can rotate multiple spindles as a unit or subunit. For this purpose, the rotating mechanism is typically adapted to rotate multiple spindles at the same speed in order to uniformly coat the ceramic deposition layer onto the rotating spindle. The rotating mechanism can consist of individual motors and gears and / or rotating belts for each spindle. More practical are gears such as elliptical belts or gear trains, or combinations thereof, which are interconnected to move each of the spindles simultaneously and at the same speed.

[0043] Furthermore, the system generally includes a first printer station, where an anode-forming layer is applied to each of the mandrels of a plurality of rotating mandrel spindle assemblies 22 of a cartridge 20, forming a plurality of anode-forming green bodies around each mandrel. A second printer station, wherein an interface forming layer is applied to each of the anode forming green bodies of the cartridge 20, thereby forming multiple multilayer green bodies around each mandrel, A third printer station, wherein an electrolyte forming layer is applied to each of the multiple rotating multilayer green bodies of the cartridge 20 to form a tubular ceramic green body, An inspection station in which the anode-forming layer, interface-forming layer, and electrolyte-forming layer are inspected for defects after their formation, and the identity of a cartridge 20 mandrel spindle assembly having any defects is identified. It includes a controller for automating the movement of cartridges from the first printer station to the inspection station, to the second printer station and the inspection station, and to the third printer station and the inspection station.

[0044] The system then includes a real-time outer diameter measuring device associated with one or more of the first, second, and third printer stations to determine the outer diameter of the ceramic formation layer applied to each mandrel spindle assembly. The real-time outer diameter measuring device can be an independent measuring device that tracks the ceramic formation layer before and after it, for example, by a printer head that sprays it. The real-time outer diameter measuring device can be a single-point measuring device so that an initial reference measurement is performed on a mandrel spindle assembly containing heat-shrinkable or disappearing tubing or coating, and the initial reference will serve as the reference for other mandrel spindle assemblies of cartridge 20. When the ceramic cleft is applied, the thickness of the applied ceramic cleft and the total thickness of the growing tubular structure or body can be determined by comparing them to the wall thickness.

[0045] Figures 3A to 3C illustrate how such measurements are performed. Figure 3A shows a cross-section of the mandrel spindle assembly 10, which has a spindle component 12 and a mandrel component 14, for example, a heat-shrinkable tube, a disappearing tube, or a coating. An outer diameter measuring device 38''' such as a laser-based device can take an initial distance measurement to the mandrel spindle assembly, which is the distance d1. Figure 3B shows a first ceramic forming layer, such as an anode forming layer 16, applied around the mandrel component 14. The measurement distance from the outer diameter measuring device 38'' to the first ceramic forming layer 16 is d2, and when subtracted from d1(d1-d2), it provides the thickness of the formed or formed first ceramic forming layer. Figure 3C shows the same or another ceramic-forming layer 16' that has been applied, which may have the same composition as the first ceramic-forming layer 16, or a different composition. The measurement from the outer diameter measuring device 38''' to this layer can be defined as d3. Therefore, the thickness d2 minus d3 (d2-d3) of the newly applied layer 16', and the total thickness d1 minus d3 (d1-d3) of the formed tubular ceramic green body can be determined. This process can be repeated for the ceramic cleft when the ceramic cleft is applied. In certain embodiments, achieving a specific thickness can induce a change in the composition of the coated ceramic-forming green body.

[0046] Another option is to measure the outer diameter of the formed tubular ceramic structure, with a C-shaped measuring device that has multiple lasers mounted on the C-shaped body to produce accurate outer diameter measurements. The C-shaped measuring device needs to be automated to center around the mandrel spindle assembly with increasing wall thickness as various ceramic baffles are applied. Such a device, after the printer head is no longer in the way, centers itself around the mandrel spindle assembly and then measures the outer diameter. Next, the measuring device can move along the longitudinal axis of the same mandrel spindle assembly to measure the outer diameter at one or more other points along the mandrel spindle assembly. After the measurement is complete, the C-shaped measuring device moves away from the cartridge so as not to obstruct the movement of the printer head.

[0047] By monitoring the outer diameter of the applied ceramic forming layer, the layer thickness can be adjusted in real time, for example, requiring the application of additional ceramic forming composition to meet dimensional specifications, and / or causing the application of different ceramic forming compositions, such as an inert forming composition. By adjusting the thickness of the ceramic formation layer in real time, it becomes possible to cover small defects, such as pits unintentionally formed in the formed layer or a previously coated layer.

[0048] In certain embodiments, the system includes a storage rack in which multiple cartridges can be stored horizontally, both vertically and horizontally, without touching adjacent cartridges above and / or below each other.

[0049] In various embodiments, the system comprises a laser cutting station and a cartridge having a rotating tubular ceramic green body, the tubular ceramic green body being exposed to a laser along the width of the tubular ceramic green body, and forming multiple tubular ceramic green bodies along a spindle having a shorter length than before exposure to the laser.

[0050] In certain embodiments, the system includes a robotic device for moving cartridges between a first printer station, a second printer station, a third printer station, an inspection station, and a laser cutting station. In certain embodiments, the robotic device moves cartridges to and from storage stations, for example, from storage stations to a first printer station, and from laser cutting stations to storage stations.

[0051] Figure 4 shows an embodiment of the system of the present invention having a storage station S, a first printer station P1, a second printer station P2, a third printer station P3, an inspection station I, and a laser cutting station LC. The system also includes a robot tray 32 that can move the cartridge 34 between various stations, as indicated by arrow lines 36 between these stations. The robot tray 32 and its movement can be controlled by a controller C, which includes a computer software program that operates the overall movement and / or control of the cartridges in the system, as well as other components of the system such as the inspection station camera and the real-time outer diameter measuring device.

[0052] The system also includes a conveyor belt assembly for moving cartridges between a first printer station, a first inspection station, a second printer station, a second inspection station, a third printer station, a third inspection station, and a laser cutting station. In certain embodiments, the conveyor belt assembly moves cartridges to and from storage stations, for example, from storage stations to a first printer station, and from laser cutting stations to storage stations.

[0053] Figure 5 shows a schematic diagram of a different embodiment of the present invention, in particular a system 40 that uses a conveyor belt 52 to move cartridges 54 along different stations, which is similar to the method described in Figure 4. However, the same inspection station cannot be easily used in a conveyor belt system (although the conveyor belt can move in the reverse direction to return to a single inspection station, such a method would prevent a single conveyor belt line having a single cartridge overall in terms of structure and inspection, as well as laser cutting, as shown in Figure 5).

[0054] Nevertheless, as can be seen in Figure 5, the system 50 includes three inspection stations I1, I2 and I3, thereby allowing the cartridge 54 to follow a straight path on the conveyor belt 52 by first moving to a first printer station P1 which includes an outer diameter measuring device 58 and a printer head 64, and then moving to a first inspection station I1 which has a camera 60. Next, the cartridge 54 moves to a second printer station P2 which has its own outer diameter measuring device 58' and printer head 64', and then moves to a second inspection station I2 which has a camera 60'. Next, the cartridge 54 moves to a third printer station P3 which includes an outer diameter measuring device 58'' and a printer head 64'', and then moves to a third inspection station I3 which has a camera 60''. Next, the conveyor belt moves the cartridge 54 to the laser cutting station LC, where the laser cutter 62 cuts the tubular ceramic green body. The operation within each station may be the same as described herein, allowing different or the same ceramic matrix to be applied to different printer stations.

[0055] In another embodiment, the present invention provides a method for producing a tubular ceramic green body, the method being A step of providing a cartridge comprising a plurality of mandrel spindle assemblies, wherein the lengths of the plurality of mandrel spindle assemblies are parallel to each other and lie in the same horizontal plane along the cartridge, the cartridge is fitted to rotate each of the plurality of mandrel spindle assemblies, each mandrel spindle assembly comprises a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a disappearing tube, or a coating on the spindle component, the outer surface of which corresponds to the inner surface of a manufactured tubular ceramic green body, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact, The steps include rotating multiple mandrel spindle assemblies and applying an anode-forming layer to each of the mandrels of each of the multiple rotating mandrel spindle assemblies of the cartridge to form multiple anode-forming green bodies around each spindle, A step of inspecting each of the multiple anode-forming green bodies for defects, The process involves rotating multiple anode-forming green bodies and applying an interface-forming layer to each of the multiple rotating anode-forming green bodies of the cartridge to form multiple multilayer green bodies around each spindle, Steps include inspecting each of the multiple multilayered green bodies for defects, The steps include rotating multiple multilayer green bodies and applying an electrolyte-forming layer to each of the multiple rotating multilayer green bodies of the cartridge to form multiple tubular ceramic green bodies around each spindle, The method includes the steps of inspecting each of a plurality of tubular ceramic green bodies for defects, and removing the spindle containing any tubular ceramic green bodies identified as having defects during inspection before firing the tubular ceramic green bodies.

[0056] This method involves monitoring the outer diameter of multiple anode-forming green bodies in real time while applying an anode-forming layer, multiple multilayer green bodies while applying an interface-forming layer, and / or multiple tubular ceramic green bodies while applying an electrolyte-forming layer.

[0057] Furthermore, this method includes storing the cartridges in a storage station, which is adapted to store multiple cartridges.

[0058] In a particular embodiment, the method includes the steps of: moving the cartridge to a first printer station to coat an anode-forming layer; subsequently moving the cartridge to a first inspection station; subsequently moving the cartridge to a second printer station to coat an interface-forming layer; subsequently moving the cartridge to a second inspection station; subsequently moving the cartridge to a third printer station to coat an electrolyte-forming layer; and subsequently moving the cartridge to a third inspection station.

[0059] In a particular embodiment of this method, at least two of the first printer station, the second printer station, and the third printer station are the same printer station. In certain embodiments, the first inspection station, the second inspection station, and the third inspection station are, for example, the same inspection station as shown in Figure 4.

[0060] In various embodiments, the method includes moving the cartridges using a conveyor belt assembly and / or using a robot.

[0061] In some embodiments, the method includes moving the cartridge from a storage station to a first printer station. In a particular embodiment of the method, after subsequently moving the cartridge to a third inspection station, the method includes moving the cartridge to a storage station.

[0062] In various embodiments, the method includes visual inspection. In some embodiments, visual inspection includes visual inspection using a camera. In certain embodiments, visual inspection using a camera includes using a computer software program to identify defects based on images from the camera. In certain embodiments, visual inspection includes maintaining records such as recording inspection information for a particular spindle of a cartridge. In some embodiments, the method includes one or more of the steps of recording the results of inspection of a plurality of anode-forming green bodies, recording the results of inspection of a plurality of multilayer green bodies, and recording the results of inspection of a plurality of tubular ceramic green bodies. In certain embodiments, the method includes recording the results of an inspection of one or more inert mammaries. Furthermore, the recorded information may include information about the layer being applied.

[0063] In some embodiments of this method, the step of applying the anode-forming layer includes the step of changing the composition of the anode-forming layer. In certain embodiments, varying the composition of the anode formation layer includes applying the anode formation layer using different printer stations. In certain embodiments, changing the composition of the anode cambium includes changing the elemental composition of the anode cambium using the same printer station.

[0064] In some embodiments of this method, varying the composition of the anode formation layer includes coating an inert formation layer and / or an active catalyst formation layer between the anode formation layers. In certain embodiments, coating an inert formation layer and / or an active catalyst formation layer between anode formation layers includes coating two or more inert formation layers and / or active catalyst formation layers, each located between anode formation layers or between one adjacent anode formation layer. In certain embodiments, the inert forming layer is a first coating layer that forms the inner diameter of the tubular ceramic green body. In various embodiments, the first layer may contain higher levels of inert and / or active catalytic material to help regulate reactivity along the cell, enhance thermal shock resistance, reduce coke formation, and, in some cases, provide some redox resistance. The anode formation layer can include many different layers of varying compositions, including an inert formation layer and an active catalyst formation layer.

[0065] In fact, the present invention includes, for example, forming an inert tubular structure for forming thin-walled ceramic tubes for reformers and / or cathode heat exchangers.

[0066] In various embodiments, the method includes recording the results of the inspection of the tubular ceramic green body and, before removing the tubular ceramic green body from the spindle, laser cutting the tubular ceramic green body along the spindle into segments of a predetermined length. In some embodiments, laser cutting yields three or four equal-length segments of a tubular ceramic green body along each spindle. In certain embodiments, the cut tubular ceramic green body can be inspected, including visual inspection, as described herein.

[0067] In some embodiments, the anode-forming layer, interface-forming layer, and electrolyte-forming layer contain a solvent. In certain embodiments, the anode-forming layer, interface-forming layer, electrolyte-forming layer, active catalyst-forming layer, and / or inert-forming layer contain a solvent.

[0068] In various embodiments, the method includes the steps of removing a tubular ceramic green from a spindle and sintering the tubular ceramic green. One or more further fabrication operations can be performed on the tubular ceramic green, such as forming one or more additional layers thereon, for example, an interlayer thin film or a cathode layer, either before or after sintering to burn off any organic matter and other materials that aid in the formation of solid tubular ceramic structures such as the tubular ceramic green.

[0069] Returning to Figure 4, in a typical operation, the robot tray 32 engages with the cartridge 34' in the storage station, moves the cartridge 34 from the storage station to the first printer station P1, and the anode-forming layer is applied to each of the mandrels of the cartridge's multiple rotating mandrel spindle assembly, forming multiple anode-forming green bodies around each mandrel. The layer coating is typically achieved by printing or spraying, such as ultrasonic atomization of the ceramic-formed layer using a printer head 44.

[0070] The composition of the anode-forming layer can be changed as the layer is applied. For example, the ceramic composition can be varied by its elemental composition (e.g., the amount of ceramic, metal oxide, and / or precious metal), or it can have a completely different composition, such as an inert layer (the anode-forming layer is composed of many different layers, each of which has a different composition). The inert layer is useful for increasing the thermal shock of the tubular SOFC and / or for absorbing or filtering contaminants. Furthermore, the activated catalyst layer can serve the latter purpose, namely, the absorption, chemical modification, and / or filtration of contaminants.

[0071] Due to the time required to coat the ceramic deposition layer, each printer station, or two or fewer printer stations, may contain a cartridge on which the ceramic deposition layer is coated onto the rotating mandrel spindle assembly. Furthermore, the system of the present invention may include three or more printer stations and / or three or more inspection stations, or two printer stations and / or two inspection stations, as well as two or more storage stations and two or more laser cutting stations. Furthermore, the number of each of these components, including storage stations, printer stations, inspection stations, and laser cutting stations, is a variety of combinations, depending in part on the composition of the ceramic green body and the timing of coating and forming the layers.

[0072] For example, multiple printers can be dedicated to coating various layers of the anode formation layer, which can make up about 70% to 80% of the tubular ceramic green body. Conversely, only one dedicated printer station is needed to coat the electrolyte layer, which can make up only about 5% to 10% of the tubular ceramic green body, is thin, and takes less time to coat.

[0073] As shown in Figure 4, the first printer station includes a real-time outer diameter measuring device 38. The real-time outer diameter measuring device 38 then determines the outer diameter of each coated ceramic formation layer in real time. Real-time monitoring can help determine when the correct amount of material was applied, and in particular, whether enough material was laid down to achieve the correct layer thickness. Furthermore, the ceramic-forming layer added afterward may repair defects in the previously applied layer and / or dimensional issues in a particular layer. In other words, by measuring dimensions in real time, it becomes possible to apply additional material to meet the specifications of a particular layer, for example, if it is measured to be thinner than specified. Therefore, a real-time outer diameter measuring device improves process efficiency and the production of working tubular SOFCs. Furthermore, this real-time outer diameter measuring device can also be used to trigger adjustments to the composition at specific wall thicknesses.

[0074] Furthermore, the anode formation layer is completed only at the first printer station, while changing the composition of the anode formation layer in the first printer. Alternatively, the anode-forming layer can be completed at the first printer station, the second printer station, and / or the third printer station (or multiple printer stations, if available). In other words, different layers of the anode-forming layer can be applied to the inert layer at different printer stations, for example, a second printer station. In such cases, the robot tray moves the cartridge from the first printer station to the second printer station and / or the third printer station. Similarly, the interface-forming layer and the electrolyte layer can be applied to one or more printer stations. These layers tend to be thinner than the anode-forming layer, but one printer is typically sufficient, especially for the electrolyte-forming layer. In certain embodiments, each printer station or subset of printer stations may have its elemental composition of the ceramic matrix layer applied adjusted for system versatility.

[0075] After the formation of the anode layer (intermittently or as needed or desired) is complete, the robotic tray can move the cartridge from the first printer station P1 (or from any printer station where the anode layer has been completed) to inspection station I, where the anode layer on the mandrel spindle assembly is inspected for defects using a camera 40 that can view, for example, an uneven, cracked, or defective ceramic layer. Furthermore, this camera 40 can be connected to a computer software program that identifies defects based on images from the camera, which is under the control of the controller.

[0076] In certain embodiments, the method of the present invention may include the step of recording the results of an inspection of a plurality of anode-forming green bodies. The record can be, for example, a digital record using a computer software program that identifies defects. The record may include cartridge identification information, location information such as spindle number, location along the length of the spindle, and type of defect, including a photograph of the defect for visual inspection by the operator. Of course, the records could be the results of inspections of multiple multilayer green bodies and / or the results of inspections of multiple tubular ceramic green bodies, and the same information could be recorded. Furthermore, the records can be used to document the inspection of intermediate ceramic formation layers, such as insert formation layers.

[0077] After inspecting the anode-forming layer, the robot tray can move the cartridge to a second printer station P2, where an interface-forming layer can be applied to each of the multiple rotating anode-forming green bodies of the cartridge, forming multiple multilayer green bodies around each mandrel. The second printer station P2 has a printer head 44' and an outer diameter measuring device 38' similar to those of the first printer station P1.

[0078] After the formation of the interface layer (intermittently or as needed or desired) is complete, the robot tray can move the cartridge from the second printer station P2 (or from any printer station where the interface layer has been completed) to inspection station I, where the interface layer on the mandrel spindle assembly is inspected for defects, similar to what is done for the anode layer. The recording of defects or the absence of such defects, and related information, can be done with respect to the first inspection of the anode formation layer.

[0079] After inspection of the interface forming layer, the robot tray can move the cartridge to the third printer station P3, where the electrolyte forming layer can be applied to each of the multiple rotating multilayer green bodies of the cartridge to form a tubular ceramic green body. The third printer station P3 has a printer head 44'' and an outer diameter measuring device 38'' similar to the first printer station P1 and the second printer station P2.

[0080] After the formation of the electrolyte-forming layer (intermittently or as needed or desired) is complete, the robotic tray can move the cartridge from the third printer station P3 (or any printer station where the electrolyte-forming layer is completed) to inspection station I, where the electrolyte-forming layer on the mandrel spindle assembly is inspected for defects in the same way as the anode-forming layer and interface-forming layer. Recording of defects or absence of defects, and related information, may be done with respect to the first inspection of the anode formation layer or the second inspection of the interface formation layer, or any intermediate ceramic formation layer that has been inspected.

[0081] After the inspection of the tubular ceramic green body containing the electrolyte cleft is completed, the robot tray can move the cartridge from the inspection station I to the laser cutting station LC, which is usually after identifying the inspection results of the tubular ceramic green body, but before removing the tubular ceramic green body from the spindle, the tubular ceramic green body can be cut along the spindle into segments of a predetermined length with the laser cutter 42. In certain embodiments, laser cutting yields two, three, four, or five segments of equal length along each spindle of the tubular ceramic green body. The laser can cut the ends of the tube evenly in a vertical manner. Lasers can also be used to cut holes in tubular ceramic green bodies. The laser can, for example, form tapered ends for manifolds and current collection. Depending on the specific application and requirements, lasers can also be used to form other shapes and apertures.

[0082] After laser cutting or formation of the tubular ceramic green body, the completed cartridge can be returned to storage station S or a second storage station (not shown) specific to the completed tubular ceramic green body. The storage station is typically temperature and humidity controlled to ensure that the integrity of the finished tubular ceramic green body is properly maintained before firing, for example, to prevent complete drying of the outer ceramic cleft.

[0083] The system of the present invention shown in Figure 4 includes a controller C that automates and controls the movement of robotic trays and / or other robotic devices necessary to move cartridges from a first printing station to an inspection station, to a second printer station and inspection station, to a third printer station and inspection station, or in any order necessary to form a desired tubular ceramic green body. The movement of the cartridges can be achieved in various ways, for example, by a wheeled robotic device, or by a device on a track or rail that can move back and forth between different components of the system to place and remove the cartridges at each station. The controller can control the rotation of the mandrel spindle assembly, which includes a subsequent ceramic formation layer on top of it. Furthermore, the controller can control the elemental composition of the ceramic matrix being coated, and can, for example, change it during coating at a single printer station. The controller can operate an outer diameter measuring device, a camera, inspection of camera images for defects, and recording of inspection results using information as described herein. Furthermore, the controller can operate the laser cutting station, including laser positioning and movement. The controller can also operate the movement of cartridges from the storage station to the first printer station, and from the laser cutting station to the storage station (for example, to a second storage station for completed tubular ceramic formed green bodies). The controller can operate the storage station and, for example, maintain the temperature and humidity of the storage station within a predetermined number or range.

[0084] Figure 5 is similar to the controller in Figure 4, but includes a controller C' that operates the conveyor belt instead of the robot; however, most other features are the same.

[0085] In another embodiment, the method of the present invention includes a method for forming a plurality of tubular ceramic green bodies, and this method is A step of providing a cartridge comprising a plurality of mandrel spindle assemblies, wherein the lengths of the plurality of mandrel spindle assemblies are parallel to each other and lie in the same horizontal plane along the cartridge, and the cartridge is fitted to rotate each of the plurality of mandrel spindle assemblies, each mandrel spindle assembly comprising a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a disappearing tube, or a coating on the spindle component, the outer surface of which corresponds to the inner surface of a tubular ceramic green body, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact, The process includes the step of laser cutting a tubular ceramic green body into a plurality of smaller tubular ceramic green bodies along each spindle.

[0086] This laser can be a carbon dioxide laser, such as a 120W CO2 laser manufactured by Trotec Laser GmbH.

[0087] In various embodiments of this method, the tubular ceramic green body contains a solvent. In certain embodiments, the multiple smaller tubular ceramic green bodies are of equal length.

[0088] <Integration by reference> The full disclosures of each patent document and scientific paper referenced herein are incorporated by reference for all purposes.

[0089] <Equal weights> The present invention may be embodied in other specific forms without departing from its spirit or essential features. Therefore, the embodiments described above should be considered illustrative in all respects, rather than limiting the inventions described herein. Therefore, the scope of the present invention is indicated by the appended claims rather than the above description, and all modifications within the meaning and scope equivalent to the claims are included.

Claims

1. A method for manufacturing tubular ceramic green bodies, A step of providing a cartridge comprising a plurality of mandrel spindle assemblies, wherein the lengths of the plurality of mandrel spindle assemblies are parallel to each other and lie in the same horizontal plane along the cartridge, the cartridge is fitted to rotate each of the plurality of mandrel spindle assemblies, each of the mandrel spindle assemblies comprises a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a disappearing tube, or a coating on the spindle component, the outer surface thereof corresponding to the inner surface of the manufactured tubular ceramic green body, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact with the cartridge, The steps include rotating the plurality of mandrel spindle assemblies, applying an anode-forming layer to each of the mandrels of the plurality of rotating mandrel spindle assemblies of the cartridge, thereby forming a plurality of anode-forming green bodies around each of the spindles, A step of inspecting each of the plurality of anode-forming green bodies for defects, The steps include rotating the plurality of anode-forming green bodies, applying an interface-forming layer to each of the rotating anode-forming green bodies of the cartridge, thereby forming a plurality of multilayer green bodies around each of the spindles, A step of inspecting each of the aforementioned multiple multilayer green bodies for defects, The steps include rotating the plurality of multilayer green bodies, applying an electrolyte forming layer to each of the rotating multilayer green bodies of the cartridge, and forming a plurality of tubular ceramic green bodies around each of the spindles, A step of inspecting each of the plurality of tubular ceramic green bodies for defects, A method comprising the step of removing a spindle containing a tubular ceramic green body that was identified as having defects during the inspection, before firing the tubular ceramic green body.

2. The method according to claim 1, comprising the step of monitoring the outer diameter of the plurality of anode-forming green bodies in real time while applying the anode-forming layer.

3. The method according to claim 1 or claim 2, comprising the step of monitoring the outer diameter of the plurality of multilayer green bodies in real time while applying the interface forming layer.

4. The method according to any one of claims 1 to 3, comprising the step of monitoring the outer diameter of the plurality of tubular ceramic green bodies in real time while applying the electrolyte forming layer.

5. The method according to any one of claims 2 to 4, wherein the step of monitoring the outer diameter in real time makes it possible to adjust the thickness of the ceramic formation layer in real time.

6. The method according to claim 5, wherein the step of adjusting the thickness of the ceramic formation layer in real time includes the step of covering small defects in a previously applied ceramic formation layer.

7. The method according to any one of claims 1 to 6, comprising the step of storing the cartridge in a storage station, wherein the storage station is adapted to store a plurality of cartridges.

8. The steps include moving the cartridge to a first printer station to coat the anode-forming layer, Next, the cartridge is moved to the first inspection station, Next, the cartridge is moved to a second printer station to apply the interface forming layer, Next, the cartridge is moved to a second inspection station, Next, the cartridge is moved to a third printer station in order to coat the electrolyte-forming layer, Next, the cartridge is moved to a third inspection station, The method according to any one of claims 1 to 7, including the method according to claim 1 to 7.

9. The method according to claim 8, wherein at least two of the first printer station, the second printer station, and the third printer station are the same printer station.

10. The method according to claim 8 or 9, wherein each of the first inspection station, the second inspection station, and the third inspection station is the same inspection station.

11. The method according to any one of claims 8 to 10, wherein the moving step includes moving using a conveyor belt assembly and / or moving with a robot.

12. The method according to any one of claims 8 to 11, further comprising the step of moving the cartridge from a storage station to a first printer station.

13. The method according to any one of claims 8 to 12, further comprising the step of moving the cartridge to the third inspection station, and then moving the cartridge to a storage station.

14. The method according to any one of claims 1 to 13, wherein the inspection step includes a visual inspection step.

15. The method according to claim 14, wherein the visual inspection step includes a step of visual inspection using a camera.

16. The method according to claim 14, wherein the step of visually inspecting using a camera includes the step of using a computer software program to identify defects based on images from the camera.

17. The method according to any one of claims 14 to 16, wherein the step of visually inspecting includes the step of maintaining the inspection information of a particular spindle of the cartridge.

18. The method according to any one of claims 1 to 17, wherein the step of applying the anode-forming layer includes the step of changing the composition of the anode-forming layer.

19. The method according to claim 18, wherein the step of changing the composition of the anode-forming layer includes the step of coating the anode-forming layer using different printer stations.

20. The method according to claim 17, wherein the step of changing the composition of the anode formation layer includes the step of changing the composition of the anode formation layer using the same printer station.

21. The method according to any one of claims 18 to 20, wherein the step of changing the composition of the anode formation layer includes the step of coating an inert formation layer and / or an active catalyst formation layer between the anode formation layers.

22. The method according to claim 21, wherein the step of coating an inert layer between anode layers comprises the step of coating two or more inert layers and / or active catalyst layers between each of the anode layers.

23. The method according to any one of claims 1 to 22, wherein the inert formation layer is the first coated ceramic formation layer of the anode formation layer.

24. The method according to any one of claims 1 to 23, wherein, after recording the results of the inspection of the tubular ceramic green body, but before removing the tubular ceramic green body from the spindle, the tubular ceramic green body is laser-cut into segments of a predetermined length along the spindle.

25. The method according to claim 24, wherein the cutting by the laser provides three or four segments of equal length along each spindle of the tubular ceramic green body.

26. The method according to any one of claims 1 to 25, wherein the anode-forming layer, the interface-forming layer, and the electrolyte-forming layer contain a solvent.

27. The method according to any one of claims 22 to 25, wherein the anode-forming layer, the interface-forming layer, the electrolyte-forming layer, and the inert-forming layer, if present, contain a solvent.

28. The method according to any one of claims 1 to 27, comprising one or more of the steps of: recording the results of the inspection of the plurality of anode-forming green bodies; recording the results of the inspection of the plurality of multilayer green bodies; and recording the results of the inspection of the plurality of tubular ceramic green bodies.

29. The steps include removing the tubular ceramic green body from the spindle, The steps include: sintering the tubular ceramic green body, A method according to any one of claims 1 to 28, including the method described in claim 1 to 28.

30. A method for forming multiple tubular ceramic green bodies, A step of providing a cartridge comprising: a plurality of mandrel spindle assemblies, wherein the lengths of the plurality of mandrel spindle assemblies are parallel to each other and lie in the same horizontal plane along the cartridge, the cartridge is fitted to rotate each of the plurality of mandrel spindle assemblies, each of the mandrel spindle assemblies comprises a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a disappearing tube, or a coating on the spindle component, the outer surface thereof corresponding to the inner surface of the tubular ceramic green body, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact; and a tubular ceramic green body around each mandrel spindle assembly; A method comprising the step of laser cutting the tubular ceramic green body into a plurality of smaller tubular ceramic green bodies along each mandrel spindle assembly.

31. The method according to claim 30, wherein the tubular ceramic green body contains a solvent.

32. The method according to claim 30 or claim 31, wherein the plurality of smaller tubular ceramic green bodies are of equal length.

33. A system for manufacturing tubular ceramic green bodies, A cartridge comprising a plurality of mandrel spindle assemblies, wherein the lengths of the plurality of mandrel spindle assemblies are parallel to each other and lie in the same plane along the cartridge, the cartridge is fitted to rotate each of the plurality of mandrel spindle assemblies, each of the mandrel spindle assemblies comprises a mandrel component and a spindle component, the mandrel component being a heat-shrinkable tube, a disappearing tube, or a coating on the spindle component, the outer surface thereof corresponding to the inner surface of the manufactured tubular ceramic green body, the inner surface defining a bore, and the spindle component being in close contact with the bore but in removable contact with the cartridge, A first printer station, wherein an anode-forming layer is applied to each of the mandrels of a plurality of rotating mandrel spindle assemblies of the cartridge, forming a plurality of anode-forming green bodies around each of the mandrels, A second printer station, wherein an interface forming layer is applied to each of the anode forming green bodies of the plurality of rotating anode forming green bodies of the cartridge, forming a plurality of multilayer green bodies around each mandrel, A third printer station, wherein the electrolyte forming layer is applied to each of the multiple rotating multilayer green bodies of the cartridge to form a tubular ceramic green body, An inspection station in which the anode-forming layer, the interface-forming layer, and the electrolyte-forming layer are inspected for defects after their formation, and the identity of a cartridge mandrel spindle assembly having any defects is identified. A system comprising a controller for automating the movement of the cartridge from the first printer station to the inspection station, to the second printer station and the inspection station, and to the third printer station and the inspection station.

34. The system according to claim 33, further comprising a real-time outer diameter measuring device associated with each of the first, second, and third printer stations for determining the outer diameter of each of the ceramic formation layers applied to the mandrel spindle assembly.

35. The system according to claim 33 or 34, comprising a storage rack, wherein a plurality of the cartridges can be stored horizontally in an up-and-down manner, but without contact with adjacent cartridges above and / or below.

36. The system according to any one of claims 33 to 35, comprising a laser cutting station, the cartridge comprising a rotating tubular ceramic green body, wherein the tubular ceramic green body is exposed to a laser along the width of the tubular ceramic green body to form a plurality of tubular ceramic green bodies along the spindle having a shorter length than before exposure to the laser.

37. The system according to any one of claims 33 to 36, comprising a conveyor belt assembly for moving the cartridge between the first printer station, the first inspection station, the second printer station, the second inspection station, the third printer station, the third inspection station, and the laser cutting station.

38. The system according to any one of claims 33 to 36, further comprising a robotic device for moving the cartridge between the first printer station, the second printer station, the third printer station, the inspection station, and the laser cutting station.

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