Method of making a fuel cell device
10355300 ยท 2019-07-16
Inventors
Cpc classification
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M8/124
ELECTRICITY
H01M4/8889
ELECTRICITY
International classification
H01M8/12
ELECTRICITY
H01M8/124
ELECTRICITY
Abstract
A fuel cell device is prepared by dispensing and drying electrode and ceramic pastes around two pluralities of removable physical structures to form electrode layers having constant width and a shape that conforms lengthwise to a curvature of the physical structures. An electrolyte ceramic layer is positioned between electrode layers, forming an active cell portion where anode is in opposing relation to cathode with electrolyte therebetween, and passive cell portions where ceramic is adjacent the active cell portion. The layers are laminated, the physical structures pulled out, and the lamination sintered to form an active cell with active passages in anodes and cathodes and passive support structure with passive passages in ceramic. End portions of at least one of the two pluralities of physical structures are curved away from the same end portion of the other of the two pluralities resulting in a split end in the fuel cell device.
Claims
1. A method of making a monolithic fuel cell device, comprising: dispensing a first paste of anode material around a first plurality of spaced-apart removable physical structures to at least partially surround each of the first plurality of spaced-apart removable physical structures with the anode material; dispensing a second paste of cathode material around a second plurality of spaced-apart removable physical structures to at least partially surround each of the second plurality of spaced-apart removable physical structures with the cathode material; dispensing a third paste of ceramic material around the first and second plurality of spaced-apart removable physical structures adjacent to the anode and cathode materials to at least partially surround each of the first and second plurality of spaced-apart removable physical structures with the ceramic material; drying the first, second and third pastes to form an anode layer and a cathode layer, wherein each of the anode layer and the cathode layer has a constant width and a shape that conforms in a lengthwise direction to a curvature of the first and second plurality of spaced-apart removable physical structures, respectively; positioning an intervening layer of ceramic material configured to function as an electrolyte in a multi-layer stack between the cathode layer and the anode layer, wherein an active cell portion of the multi-layer stack is formed by the anode material of the anode layer in opposing relation to the cathode material of the cathode layer with the intervening layer of ceramic material therebetween, and passive cell portions are formed by the ceramic material adjacent to the active cell portion in each of the anode layer, cathode layer and intervening layer; laminating the multi-layer stack; pulling the first and second plurality of removable physical structures out of the laminated multi-layer stack to reveal spaced-apart active passages formed through the active cell portion of each of the anode layer and the cathode layer and spaced apart passive passages formed through the passive cell portion of each of the anode layer and the cathode layer; and sintering the laminated multi-layer stack to form an active cell comprising the spaced apart active passages embedded in and supported by the sintered anode material and sintered cathode material and a passive support structure comprising the spaced apart passive passages embedded in and supported by the sintered ceramic material and that transition integrally to the active passages within the active cell, wherein at least one end portion of at least one of the first and second plurality of spaced-apart removable physical structures is curved in a direction away from the same end portion of the other one of the first and second plurality of spaced-apart removable physical structures resulting in a split end in the fuel cell device to which separate gas inputs can be coupled.
2. The method of claim 1, wherein both end portions of both the first and second plurality of spaced-apart removable physical structures are curved with both same end portions being curved away from each other resulting in both ends of the fuel cell device being split whereby separate gas inputs and separate exhaust outputs can be coupled to the ends of the fuel cell device.
3. The method of claim 2, wherein the separate gas inputs for the anode layer and the cathode layer are at opposite ends and the separate exhaust outputs for the anode layer and the cathode layer are at opposite ends.
4. The method of claim 2, wherein the separate gas inputs for the anode layer and the cathode layer are at the same end and the separate exhaust outputs for the anode layer and the cathode layer are at the same end opposite the end for the separate gas inputs.
5. The method of claim 1, wherein only one end portion of only one of the first and second plurality of spaced-apart removable physical structures is curved, while a remaining portion of the only one of the first and second plurality of spaced-apart removable physical structures and the entire other of the first and second plurality of spaced-apart removable physical structures are straight resulting in the split end at only one of the ends of the fuel cell device to which separate gas inputs can be coupled, whereby gas exhaust outputs are at the opposite end that is not split.
6. The method of claim 1, wherein only one end portion of each of the first and second plurality of spaced-apart removable physical structures is curved, while a remaining portion of each of the first and second plurality of spaced-apart removable physical structures is straight.
7. The method of claim 6, wherein the end portions are curved at the same end of the fuel cell device resulting in the split end at only one of the ends of the fuel cell device to which separate gas inputs can be coupled, whereby gas exhaust outputs are at the opposite end that is not split.
8. The method of claim 6, wherein the end portions of the first plurality of spaced-apart removable physical structures are curved at one end of the fuel cell device and the end portions of the second plurality of spaced-apart removable physical structures are curved at the opposite end of the fuel cell resulting in both ends of the fuel cell device being split whereby separate gas inputs and separate exhaust outputs can be coupled to the ends of the fuel cell device.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with a general description of the invention given above, and the detailed description given below, serve to explain the invention.
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DETAILED DESCRIPTION
(21) Reference may be made to the following patents and publications by the same inventors, which describe various embodiments of a multilayer Fuel Cell Stick device 10 (et al.), the contents of which are incorporated herein by reference: U.S. Pat. Nos. 8,278,013, 8,227,128, 8,343,684, and 8,293,415, and U.S. Patent Application Publication Nos. 2010/0104910 and 2011/0117471. The inventive structures and/or concepts disclosed herein may be applied to one or more of the embodiments disclosed in the above-referenced published applications.
(22) Various material terms will be used interchangeably, regardless of the stage of the material during manufacturing. For example, anode 24, anode layer 24, anode material 24, etc. all refer to the anode itself or the layer in which one or more anodes are positioned, irrespective of whether the anode material is in the form of a paste, a preform layer, a sintered layer, an initial green state, or a final fired state.
(23) In accordance with the present invention, to form the passive and active passages in multilayer fuel cell devices, removable physical structures, such as wires, are placed in the anode and cathode layers of the device as the layers are assembled in the green state. The removable physical structures travel from one end of the device, through the active area, and are spaced apart from one another with the anode or cathode material therebetween. Previous designs used removable physical structure at the ends of the device to form the passive passages, which were coupled to larger areas of organic sacrificial material that were used inside the device to form the active passages. The wires were simply placed between preformed sheets of green ceramic material with one end in contact with the sheet of sacrificial material and the other end extending outside the end of the device. After lamination, during which the preformed sheets conform to the shape of the physical structures, the removable physical structures were pulled out, and then the device was co-fired, allowing the sacrificial material to burn out and exit the end of the device through the passive passages and/or through other temporary bake-out ports in the sides. Despite embodiments that use ceramic balls in the active area to help support the active passages, the large flat active passages, as shown in
(24) In the present method, the active area is assembled with removable physical structures, such as fine wires, for example, 0.01 inch (0.254 mm), that are spaced apart and surrounded by solid material. In other words, the removable physical structures are at least partially surrounded by solid material so as to embed them within a layer of green material, rather than placed between preformed layers. The removable physical structures will be referred to as wires, interchangeably for ease of discussion, with the understanding that the invention is not limited to wires as the only possible removable physical structures. Removable physical structures are distinguished from sacrificial materials that burn out at elevated temperatures, and refer instead to solid structures that are pulled out of the device.
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(26) Once the device stack is formed, it is laminated, and then the wires 92 are removed. The layer-by-layer dimensions are better maintained during lamination with the present invention because the green preform layers already contain the wires 92 with the electrode material surrounding and conforming to the wire shape, such that the green layers need not conform around the wires 92 as the layers are pressed together. The result, for a single active cell 50, is shown in cross-section in
(27) In the active cell 50, different combinations of materials can be used in combination with the wires 92.
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(29) When coating the wires with the desired material to form a layer having the plurality of spaced-apart passages embedded therein, the material can completely cover or not completely cover the wires, and the proper choice of the coating conditions can help achieve the optimal performance. Having a majority of the wire 92 surrounded by the material of the layer achieves the objective of providing support for the structure.
(30) If the surrounding material does not exceed the top and bottom of the wires having a round shape, the intervening support material is a pillar shaped structure. This is the minimum structure necessary to give a solid support structure in the active area, such that it is not required that the passages be completely encompassed within the electrode, only mostly encompassed by virtue of being essentially sandwiched between support structures. The support material can meet the wire exactly at the top and bottom surfaces or the support material can be recessed on both sides of the wires, either way forming a pillar structure. Additionally, an asymmetric structure can be formed where one side of the wires is exceeded and one side is not. By way of example, the pillar form, and in particular the recessed pillar form, can be created by using a paste that becomes much thinner as the solvent dries out of the polymer matrix or by shaving the top surface with a thin razor blade and distorting down between the wires.
(31) As opposed to varying the material composition in the thickness direction of the wires,
(32) With respect to the wires 92 or other physical structures, variations are possible in terms of wire diameters, wire materials, and wire properties. The wires can be 0.02 inch, 0.01 inch, 0.005 inch, or 0.002 in, for example. The wires can be made of stainless steel, carbon steel, nickel, titanium, or any other appropriate material. The wires can be spring metal, annealed, flexible and have varying degrees of strength. The wires can be straight or curved, as discussed further below. The wires can be round, oval, semi-circular, square, rectangular, or any other shape, as desired. The plurality of wires in a single layer need not all be of the same shape or dimension, and can be different in one layer versus another layer. Additionally, the wires can change in dimension and/or shape as they travel down the length of the device. For example, a wire can have a first diameter along the length of the passive area of the device and gradually or sharply decrease to a second diameter in the active area of the device, for example, a smaller second diameter. In another example, the wire can have a first shape along the length of the passive area of the device and gradually or sharply change to a second shape in the active area of the device, such as a first round shape and a second semi-circular shape or a second oval shape. The changes in diameter and shape may be designed to achieve objectives in gas flow properties and/or to achieve less resistance to the wires being removed after lamination. It may also be advantageous to heat the device after lamination to facilitate the wire removal, for example, to about 85 C., although other temperatures are contemplated. In one embodiment, the temperature of the device is raised to above the glass transition temperature (T.sub.g) of the organic materials of the stick to dramatically soften the material, allowing easy removal of the wires. Additionally, the wires may be coated, as necessary with a release agent. However, the use of heat may make the use of release agents unnecessary. Wires may be used to form any combination of input passages, active passages, and exhaust passages. Further, within a single layer, such as an anode layer 24, the wires 92 may be arranged in parallel in a single layer, or multiple spaced layers. The size of the wires, and thus the size of the formed passages, may also be varied in the multiple spaced layer, for example, a row of smaller diameter passages could be formed in anode layer 24b of
(33) Various methods are possible for connecting the gas supplies to the fuel and air passages. In an elongated device, a fuel supply can be coupled to one end, and an air supply to the opposite end, for example, by placing flexible supply tubes over the ends. In such embodiments, the fuel entering one end would have to exit the device at a point before reaching the opposite end, since the opposite end is coupled to the air supply. Thus, side exits or vertical exits have been contemplated in previous designs. When using wires 92 to form the passages 14, 20 to and through the active area 50, the wires for forming the fuel passages, 14, for example, can extend lengthwise from a fuel input end of the device and terminate at the conclusion of the active area, or can proceed into the opposite passive area but stop short of the opposite air input end. A side exit path can then be formed using sacrificial material or additional wires in contact with the lengthwise wires, such as at the ends of the wires, and extending widthwise to the side of the device.
(34) Alternatively, the wires can extend through the entire length of the device, such that both the fuel and oxidizer passages 14, 20 extend from a first end 11a to a second end 11b, but then one of the set of passages 14 or 20 is sealed off at each end, such as by injecting a small amount of ceramic or glass paste into the passages at the ends to plug them and seal them off, or by temporarily plugging the passages to be kept with short wires and painting a paste of ceramic or glass over the passages to be sealed, drying the paste, then removing the temporary plugs. Exit passages to the sides or vertically would still need to be formed then ahead of the plugs. In yet another alternative, where the wires extend the full length of the device, supply of the gases may be made by a plurality of supply tubes, for example, ceramic tubes, that are sized to be inserted into the respective plurality of passages, in typical manifold fashion, but advantageously outside the furnace in the cold end region of the device.
(35) In alternative embodiments, shown in
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(38) To better provide for separate fuel and air connections,
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(42) The use of filled or plugged via holes can provide a potential source of gas leaks, which negatively affect device performance, so an alternate embodiment is shown in exploded view in
(43) In the embodiments of
(44) It was discussed above that the paste material deposited around the wires 92 can be varied in the length direction, for example, as shown in
(45) One method for forming internal series connections is to include an interconnect tab 54 for each electrode segment, as shown in
(46) Referring to
(47) The various series designs enable any number of active cells, whether situated in a single active layer sequentially down the length, or vertically by stacking active cells on top of each other, or a combination of both. Thus, small devices or large devices can be provided with relatively high voltage. For example, a handheld electronic device could be provided with the design of
(48) While the present invention has been illustrated by the description of one or more embodiments thereof, and while the embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and method and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.