The present invention relates to an improved cell unit and to a cell stack comprising a plurality of such cell units, as well as a method of manufacturing the same. The present invention more specifically relates to metal-supported cell units and stacks thereof, and more specifically still metal-supported solid oxide fuel cell (MS-SOFC) units and stacks thereof and metal-supported solid oxide electrolyser cell (MS-SOEC) units and stacks thereof.
Solid Oxide Fuel Cells
Fuel cell units use an electrochemical conversion process that oxidises fuel to produce electricity. They may be tubular or planar in configuration. A solid oxide fuel cell (SOFC) is based upon a solid oxide electrolyte that conducts negative oxygen ions from a cathode to an anode located on opposite sides of the electrolyte. For this, a fuel, or reformed fuel, contacts the anode (fuel electrode) and an oxidant, such as air or an oxygen rich fluid, contacts the cathode (air electrode).
Significant challenges in mechanical, electrical and thermal design are encountered when designing SOFC stacks. For example, in a planar SOFC stack arrangement, a stack of cells is typically arranged in a stacking direction from one end of the stack (e.g. from a base plate end) to the other end (e.g. to an end plate end). The operating performance of the fuel cells/fuel cell stack repeat layers are affected by temperature and other factors.
Metal Supported Solid Oxide Fuel Cells
Conventional ceramic-supported (e.g. anode-supported) SOFCs suffer from low mechanical strength and are vulnerable to fracture. Metal-supported SOFCs (MS-SOFCs) have recently been developed which have the active fuel cell component layer supported on a metal substrate. In these cells, the ceramic layers can be very thin since they only perform an electrochemical function (i.e. they are not self-supporting). Such metal supported SOFC stacks are more robust, have a lower cost, and also exhibit better thermal properties. They can also be manufactured using conventional metal welding techniques.
WO2015/136295 describes metal-supported SOFCs in which the electrochemically active layer (or active fuel cell component layer) comprises anode, electrolyte and cathode layers respectively deposited on, and supported by, a metal support plate 120 (e.g. foil). As shown in
In a MS-SOFC, the metal substrate may be an intrinsically porous metal substrate formed from a powder metal precursor (for example, by tape casting), or, more preferably, is formed from a metal support plate provided with a porous region in the form of through holes or small apertures surrounded by a non-porous (solid) region. The porous region 124 is provided through the metal support plate 120, and an anode layer 113 (or cathode 111, depending on the polarity orientation of the electrochemically active layer 110) is coated over that region, and then successive layers coated on top, which layers are thus supported by the metal support plate 120. As shown, the electrolyte layer usually is coated over the side edges of the innermost electrode and extends over the metal substrate thereby sealing the gas within the porous region and innermost electrode. The porous region allows the fluid volume 140 (defined by the adjacent plates 120, 150 and spacer plate 130) to be in fluid communication with the electrochemically active layers 110 on the support plate 120 through the small apertures. As shown, the electrolyte layer usually is coated over the side edges of the innermost electrode and extends over the metal substrate (as extended layer 123) thereby sealing the gas within the porous region and innermost electrode.
In the separator plate 150, up and down corrugations are provided to extend up to the cathode 111 (or anode 113, depending on the polarity orientation of the electrochemically active layers 110) of a subsequent fuel cell unit 90 stacked onto this fuel cell unit, and down to the metal support plate 120 of its own fuel cell unit. This electrically connects between adjacent fuel cells units 90 of a stack to put the electrochemically active layers 110 of the stack (usually one on each fuel cell unit) in series with one another. Other pressed three dimensional features such as round or elongate dimples (or troughs and peaks) extending from each side would also be suitable to provide electrical contact and structural support (resisting stack compression forces).
Other teachings of fuel cells, fuel cell stacks, fuel cell stack assemblies, and heat exchanger systems, arrangements and methods can be found in WO2002/35628, WO2003/07582, WO2004/089848, WO2005/078843, WO2006/079800, WO2006/106334, WO2007/085863, WO2007/110587, WO2008/001119, WO2008/003976, WO2008/015461, WO2008/053213, WO2008/104760, WO2008/132493, WO2009/090419, WO2010/020797, WO2010/061190, and WO2015/004419.
A solid oxide electrolyser cell (SOEC) may have the same structure as an SOFC but is essentially a solid oxide fuel cell operating in a regenerative mode to achieve the electrolysis of water and/or carbon dioxide by using the solid oxide electrolyte to produce hydrogen gas and/or carbon monoxide and oxygen. In a SOFC fuel (for example, hydrogen gas) is provided by a fuel port and is used by the cell, whereas in a SOEC the cell produces, for example, hydrogen gas which is collected at the fuel port.
The present invention is directed at stack repeat solid oxide cell units having a structure suitable for use as an SOEC or SOFC. For convenience, SOEC or SOFC cell units will both hereinafter be referred to as “cell units” (i.e. meaning SOEC or SOFC cell units).
There is a continual drive to increase the cost-efficiency of fuel cells—reducing their cost of manufacture would be of significant benefit to reduce the entry cost of fuel cell energy production.
According to an aspect there is described a metal-supported, planar cell arrangement, the metal-supported, planar cell arrangement comprises: at least one pair of cells, each cell comprising a metal substrate having first and second sides and a porous region providing fluid communication between the sides, planar cell chemistry layers comprising fuel electrode, electrolyte, and air electrode layers being coated or deposited over, and supported by, the porous region on the first side; wherein: the metal substrates are in a stacked arrangement with their cell chemistry layers overlying each other such that either both their first sides, or, both their second sides face inwardly in a spaced, opposed relationship, the inwardly facing sides thereby defining a common first fluid volume between them for one of fuel or oxidant.
The invention relates to a metal-supported, planar cell arrangement, that is to say, a cell arrangement in which the cell chemistry layers are planar (extending only in a single plane) and non self-supporting i.e. they only exist as thin coatings or films respectively deposited over and (integrally) supported by the porous metal substrate. This is in contrast to anode-supported, or cathode-supported, or electrolyte-supported cells where the cell chemistry layers form rigid, self-supporting tiles that can exist alone and be mounted or attached to other support structures. The invention particularly relates to metal supported, solid oxide fuel cells “MS-SOFCs” or solid oxide electrolysis cells “MS-SOECs”.
The porous metal substrate only supports cell chemistry layers on its first side; the second side of each substrate does not support any cell chemistry layers, rather the second sides face each other and are exposed to the common volume or space between them that enables a first fluid to be supplied to the innermost electrode (closest to the supporting metal substrate) on each first side.
The (active) cell chemistry layers are planar and hence, at least the portion of the metal substrate supporting that chemistry is planar as well. The cell chemistry layers are laid up in the same order over each region such that the metal substrates define a common first fluid volume that may act as a fuel volume where each cell has a fuel electrode closest to the supporting metal substrate, or that may act as an oxidant volume where each cell has an air electrode closest to the supporting metal substrate. Within the stacked arrangement the cell chemistry layers lie above and below each other (e.g. in parallel planes), and will usually be laterally aligned with each other (i.e. in register with each other).
The two fuel electrodes may be electrically connected and the two air electrodes of the pair of cells may be electrically connected. Usually, the innermost electrodes (closest to the supporting metal substrate) are electrically connected by virtue of an electrical connection between the two respective opposed metal substrates. The two outermost electrodes are connected by connection between the 2 respective current collectors on the outermost electrodes.
The metal substrates may be sealingly connected together around a periphery thereof.
Preferably, the pair of metal substrates comprise two separate metal plates that are connected together either directly or indirectly to form the stacked arrangement, for example, such that each metal plate itself has an integral porous region (bounded by a non-porous region) and supports cell chemistry layers coated on the porous region. Usually, the two separate metal plates are identical.
In one embodiment, the two metal plates are connected together indirectly to form the stacked arrangement, optionally with a (flat) metal spacer plate disposed between them. The two metal plates and intermediate metal spacer plate may be sealingly connected together, at least around a periphery thereof, for example, by welding through all three components.
When a spacer is disposed between the two separate metal plates, this has the disadvantage of an extra component being required in the stack, but has the advantage that flat planar metal plates may be used upon which the cell chemistry layers may conveniently be directly laid down by conventional coating or spraying deposition techniques. The spacer may comprise a frame or flat peripheral component (positioned beyond the active cell chemistry region) that is sandwiched between flat metal substrates and that creates a volume for, and sealingly surrounds, the first fluid volume.
Usually, there should not be any significant structure within the fluid volume that would obstruct flow but a further spacer component in the form of an open or very permeable structure could be provided where the cell chemistry is provided that may support and/or contact the substrate (or chemistry).
Alternatively (to indirect connection of substrates), the two metal plates may be connected together directly so that they abut one another to form the stacked arrangement, one or both of the metal plates having inherent shaped features (for example, flanged perimeter features) that create the first fluid volume between the plates. The two metal plates may be sealingly connected directly together, at least around a periphery thereof, for example, by welding. This reduces the number of components, as a spacer is not required, thereby reducing material wastage. It may also conveniently electrically connect the two metal plates.
Alternatively (to separate substrates), the metal substrates are formed as a single continuous metal substrate having a first side upon which the pair of cell chemistry layers are respectively coated or deposited over the porous regions, the continuous metal substrate being folded (e.g. through 180 degrees) between the cell chemistry layers so that they overlie each other to form a folded pair of cells defining the first fluid volume for the one of fuel or oxidant. Conveniently, the innermost electrodes (i.e. closest to the supporting metal substrate) are electrically connected by virtue of the continuous metal substrate. Such a design also inherently requires less components and less welds/sealing.
The continuous metal substrate may be folded through 180 degrees, the 180 degree fold may take the form of two 90 degree folds separated by a short section of continuous metal substrate which, in turn, assists in defining the common fluid volume enclosed by the continuous metal substrate. As described elsewhere, shaped features or a spacer may be provided to support the substrates and maintain an open common fluid volume.
Preferably, the arrangement further comprises multiple folded pairs of cells stacked adjacent one another in a bank of cells. In the bank, the innermost electrodes (closest to the supporting metal substrate) may be electrically connected by virtue of the continuous metal substrate, and the outermost electrodes may be electrically connected by means of current collecting structures. The current collecting structures may be permeable support structures, and need only be exposed to one fluid environment, which is the same fluid environment over its surface area. This reduces the thermal and chemical requirements of the current collecting structures.
Preferably, in the bank, each folded pair of cells is formed from a separate respective metal substrate, which substrate is folded once so that it has only one folded end, the first fluid volume being disposed inside the folded substrate.
Alternatively (to separate substrates), in the bank adjacent folded pairs of cells are formed from a common continuous metal substrate, which substrate is folded multiple times so that it has multiple opposite folded ends. Such a substrate may define multiple respective first fluid volumes for the one of fuel or oxidant. Such volumes may alternate with respective second fluid volumes for the other of fuel or oxidant.
Preferably, at least one of the metal substrates comprises flanged perimeter features, and the metal substrates are sealed together around the flanged perimeter features to form the common first fluid volume therebetween. The flanged perimeter features may be formed by pressing the substrates into a concave configuration. Both of the metal substrates of the pair of cells may comprise flanged perimeter features.
Preferably, at least one fluid port, usually at least one inlet port and at least one outlet port, is provided as an opening through each of the metal substrates, the respective fluid ports being aligned with each other in the direction of stacking and in communication with the common first fluid volume. Alternatively, the at least one fluid port is in communication with the common second fluid volume. Alternatively, at least a first fluid port is in communication with the common first fluid volume and at least a second fluid port is in communication with the common second fluid volume. The at least first fluid port and the at least second fluid port may deliver a first fluid to the first fluid volume and a second fluid to the second fluid volume, respectively. At least a first exhaust port may be in communication with the common first fluid volume, and at least a second exhaust port may be in communication with the common second fluid volume. The at least first exhaust port and the at least second exhaust port may extract a first exhaust fluid from the first fluid volume and a second exhaust fluid from the second fluid volume.
Preferably, at least one of the metal substrates is provided with shaped port features formed around its port that extend inwardly within the common first fluid volume, elements of the shaped port features being laterally spaced from one another to define fluid pathways between the elements from the port to enable passage of fluid from the port to the common first fluid volume. The shaped port features are also preferably formed by pressing.
At least one of the metal substrates may be provided with shaped port features formed around its port that extend outwardly away from the common first fluid volume. Where multiple such pairs of cells are stacked adjacent one another, such features may serve laterally to locate a sealing gasket provided between the pairs of cells, or such features may interface with an adjacent plate to form a hard stop to limit compression of a gasket provided between the pairs of cells, or may form a surface upon which a seal may be formed in situ from a sealing paste or the like. Within a bank of cells, metal substrates may be electrically connected together and so such shaped port features may be welded to those of adjacent cells conveniently providing both an electrical connection and enabling sealing of the ports/manifolds.
A support structure may be provided within the common first fluid volume in order to help maintain a spacing between the opposed respective inwardly facing sides where the compressive force for current collection are low or the cells are sufficiently stiff.
The support structure may be a permeable support structure, and need only be exposed to one fluid environment, which is the same fluid environment over its surface area. This reduces the thermal and chemical requirements of the support structures. The innermost electrodes (closest to the supporting metal substrate) may be electrically connected by virtue of the metal substrate, and the outermost electrodes may be electrically connected by means of current collecting structures. The current collecting structures may be permeable support structures, and need only be exposed to one fluid environment, which is the same fluid environment over its surface area. This reduces the thermal and chemical requirements of the current collecting structures.
The support structure within the common first fluid volume may be provided with a catalyst in order to promote internal reforming, for example when the common first fluid volume is a fuel volume. If a support structure is not provided within the common first fluid volume, such a catalyst may be provided on the metal substrate surface, for example when the common first fluid volume is a fuel volume.
Preferably, the inwardly facing sides define a first fluid volume for fuel. The inwardly facing sides are usually the second sides of the metal substrates. In that arrangement, the cell chemistry faces outwardly and current may be conveniently collected from the outermost electrodes.
Usually, the fuel electrode layer will be the first layer of the cell chemistry layers deposited on the first side of the metal substrate. Where the inwardly facing sides define a first fluid volume for fuel (when operated as a SOFC), the inwardly facing side will thus be the second side of the metal substrate, and the fuel gas will pass through the porous region from the second side to the first side so as to contact the fuel electrode layer.
In an alternative cell arrangement, the inwardly facing sides define a first fluid volume for oxidant. In this case, if again the fuel electrode layer is the first layer of the cell chemistry layers deposited on the first side of the metal substrate, the inwardly facing side will thus be the first side, such that the cell chemistry layers are within the common first fluid volume, and the air electrode layer will be exposed to the first fluid volume for oxidant. In that arrangement, the outermost electrodes are located within the substrates necessitating careful insulation of any device collecting current from the substrates themselves (at the opposite potential).
Preferably, multiple pairs of cells are stacked adjacent each other to form a bank of cells, whereby at least one second fluid volume is defined between adjacent pairs of cells, and the first fluid volume is for either fuel or oxidant and the at least one second fuel volume is for the other of fuel or oxidant. This means that alternating first and second fluid volumes are defined along the stacking direction. Hence, the other respective sides of the metal substrates, which face outwardly in a respective pair of cells of the bank are in a spaced, opposed relationship with counterparts in an adjacent respective pair of cells. Usually, the first fluid volume is defined between metal substrates in the pair of cells, and the second fluid volume is defined between the adjacent pairs.
In the bank, adjacent first fluid volumes may be in fluid communication with each other via openings provided through the respective metal substrates, which openings are aligned in the stack direction to form internal passageways (manifolds) within the bank. The same may apply to the second fluid volumes. However, one of the two fluid volumes may have externally manifolded inlet and/or outlet ports. The internal passageways may be sealingly defined by gaskets provided between the pairs of cells in the bank.
A support structure may be present within the common first fluid volume and may be provided with a catalyst in order to promote internal reforming, for example. If a support structure is not provided within the common first fluid volume, such a catalyst may be provided on the metal substrate surface, for example when the common second fluid volume is a fuel volume.
Preferably, all the fuel electrodes in the bank are electrically connected and/or all the air electrodes in the bank are electrically connected. This means that the electrodes of one type are connected in parallel. This leads to a relatively increased current output of the bank.
In a highly preferred arrangement, all the respective pairs of cells in a bank are welded together, the substrates thus all being electrically connected. The welding may be conducted during layup as each cell is added to the stack.
Preferably, the metal substrates and cell chemistry layers are laid out with side edges, and the connected fuel electrodes and/or air electrodes are connected along the same side edges.
Preferably, the fuel electrodes in one bank are connected in series to the air electrodes of a next adjacent bank. This leads to a relatively increased voltage output of the banks of fuel cells.
Preferably, an insulating sheet is disposed between adjacent banks to prevent direct electrical contact between the (e.g. outermost electrodes of the) adjacent banks. For example, with the banks connected in series there may be an electrical connection between the last substrate of one bank and the outermost electrode of the adjacent bank
In one embodiment, a single cell is provided at an end of a bank, and that cell makes direct electrical contact with an adjacent bank (for example, between the substrate of the single cell and the outermost electrode of the adjacent bank) so as to connect the adjacent banks in series.
Such a single or unpaired cell may comprise a metal substrate with active cell chemistry layers on it that is attached to a non-porous metal sheet to form an end coupon (for example, by welding to form the end coupon with an enclosed fluid volume). The metal sheet may be, for example, an undrilled metal substrate that may also be flat and unformed. Advantageously, in this way, adjacent banks may be connected in series, with face to face contact over a large portion of the cell area, without the need for additional electrical connections. For example, one bank may have its interconnectors all connected in parallel and the outermost interconnect may contact (physically and electrically) and make a series connection with a non-porous metal sheet of an end coupon of the adjacent bank. In that adjacent bank, the non-porous metal sheet and substrate are at the same potential and are connected in parallel to all the other metal substrates in that bank. Thus, parallel connected substrates in the adjacent bank are connected by a series connection to parallel connected interconnectors in the first bank.
According to a further aspect, there is described a method of assembly of a metal-supported, planar cell arrangement, the method comprises: providing first and second cells, each comprising a metal substrate having first and second sides and a porous region providing fluid communication between the sides, planar cell chemistry layers comprising fuel electrode, electrolyte, and air electrode layers being coated or deposited over, and supported by, the porous region on the first side; and inverting one of the cells with respect to the other so that the metal substrates are in a stacked arrangement with their cell chemistry layers overlying each other such that either both their first sides, or, both their second sides face inwardly in a spaced, opposed relationship so as to define a common first fluid volume therebetween for one of fuel or oxidant, so as to form the cell arrangement.
The method may comprise electrically connecting either the two fuel electrodes or the two air electrodes of the pair of unit cells. In a continuous substrate such a substrate may provide the connection.
Thus, a repeating unit comprising a pair of cells can be manufactured which define a common first fluid volume therebetween.
Preferably, the metal substrates are formed as a single continuous metal substrate, and the inverting comprises folding the continuous metal substrate between the cell chemistry layers so that they overlie each other to form a folded pair of cells defining the first fluid volume for the one of fuel or oxidant. The folding may be through 180 degrees, and may comprise two 90 degree folds separated by spacing corresponding to the desired height of the first fluid volume.
Preferably, the cell chemistry layers of the pair of cells are respectively coated or deposited over the porous regions first side, and the metal substrate is subsequently folded. Coating or depositing followed by folding conveniently means that the substrate need not be turned over to coat or deposit the cell chemistry layers of the pair of cells, and means that the cell chemistry layers of the pair of cells can be coated or deposited in the same manufacturing process.
Preferably, a pre-fold is created on the metal substrate prior to coating or depositing the cell chemistry layers. The pre-fold is a precursor to the fold, positioned in the desired location of the fold or folds, and the cell chemistry layers of the pair of cells is subsequently coated or deposited to either side of the pre-fold. The pre-fold may be created by stamping or scoring a continuous or discontinuous line across the metal substrate. Two pre-fold lines are created if the fold comprises two 90 degree folds. Further pre-fold lines may be created as precursors to a substrate folded multiple times. The pre-fold creates a line of weakness along which the substrate is more susceptible to folding during the folding step, after coating or depositing of the cell chemistry layers, which reduces the possibility for damaging the cell chemistry layers in the process of folding the substrate. That is, the pre-fold creates a line of weakness.
A step of flattening may follow the step of creating a pre-fold. The flattening ensures that the substrate is sufficiently flat for coating or deposition of the cell chemistry layers.
Preferably, the method further comprises cutting openings through each of the metal substrates to form at least one inlet port and at least one outlet port.
Thus, ports for fluid delivery are formed in each metal substrate. Upon folding and/or stacking of the metal substrates, the respective fluid ports being aligned with each other in the direction of folding and/or stacking and in communication with the common first fluid volume. Further ports may similarly be in communication with the second fluid volume.
Preferably, at least one of the metal substrates is pressed around its port to form shaped port features that extend inwardly within the common first fluid volume or that extend outwardly away from the common first fluid volume.
In a subsequent step, the metal substrates may be sealed together around part or all of their periphery (e.g. around one, two, three or all four sides) by a flanged perimeter or separate spacer component. In the case of a folded continuous substrate, a folded side may or may not require a flanged perimeter. A subsequent step of welding or brazing around the flange may be used. This step of welding or brazing around the periphery seals the first fluid volume from the remaining environment which may or may not be in communication with the second fluid volume.
The step or steps of pressing provide a concavity for the first and/or second fluid volumes. The flange around the periphery and the shaped port features that extend inwardly within the common first fluid volume may be formed in the same or separate pressing steps. The steps of pressing and cutting may be made before or after the step of coating or depositing the cell chemistry layers; preferably the steps of pressing and cutting may be made before the step of coating or depositing the cell chemistry layers to prevent damage to the cell chemistry layers.
Preferably, a further cell arrangement is provided in the same manner as the first cell arrangement, the cell arrangements are stacked into a bank and electrical connections between fuel electrodes within a bank, and/or, air electrodes within a bank are provided. A further step may comprise stacking the respective banks of cells to form a stack of cells. An insulator may be provided between adjacent banks such that the respective end cells in adjacent banks are not connected in series. Alternatively, adjacent banks may be connected in series where a single cell is provided at an end of a bank.
Preferably, the metal substrates are generally rectangular, and the port holes are provided at left and right ends thereof with cell chemistry layers in a central region facing outwardly from each pair of metal substrates, and an electrical conducting and fluid conducting spacer is laid over the uppermost chemistry layer (outermost electrode), in contact with the chemistry layer and separated from the metal substrate, to provide electrical contact to a chemistry layer of another cell to be placed on top in a stacked arrangement, and the spacer is provided with electrical connections at the front and/or rear edges thereof, perpendicular to the disposition of the port holes. Preferably, the conducting spacer is separated from the underlying metal substrate by an extended area of electrolyte surrounding the central region and acting as an insulator.
A list of the reference signs used herein is given at the end of the specific embodiments. Repeat use of reference symbols in the present specification and drawings is intended to represent the same or analogous features or elements.
It will be apparent to those of ordinary skill in the art that various modifications and variations can be made in the present invention without departing from the scope of the invention. For instance, features described as part of one embodiment can be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents.
In the following description, air is used as the oxidant. Any reference to “oxidant” elsewhere can therefore be construed as a reference to “air”, and vice versa.
Referring to
As in
The anode layer 113, electrolyte layer 112, and cathode layer 111 may be formed by deposition, e.g. chemical vapour deposition, electrostatic deposition, spray deposition, spin-on deposition, powder deposition or the like, onto the planar metal substrate 120. The process may be a two-stage process, with deposition of powder or granular material followed by sintering or other treatment to form each of the layers of the solid oxide cell. Each layer is a thin layer such that none of the layers is self-supporting; that is to say, the metal substrate is required to give support to the solid oxide chemistry layers. Other barrier layers may also be provided, for example an extended electrolyte layer 123. As with the prior art cell, the electrolyte layer is coated over the side edges of the innermost electrode and extends over the metal substrate thereby sealing the gas within the porous region and innermost electrode.
In
To explain, fuel (e.g. hydrogen or hydrocarbon gas) needs to contact the fuel electrode or anode (in an SOFC) side of the cell unit and oxidant (e.g. air or oxygen) needs access to the air electrode or cathode side of the cell unit. Accordingly, when the anode is adjacent the metal substrate, the fluid volume between the support plates (in this case the “first fluid volume”) is preferably for fuel. However, in a back-to-back arrangement, if a cathode layer 111 were instead to be deposited first, the first fluid volume would need to be an oxidant fluid volume.
Support structure 131 may be similar to interconnect 160 of
The support structure 131 need not be conductive, though it may be conductive. This is because the spacers 130 (which separate the two metal substrates in the arrangement of a pair of cell units) may be conductive, thus allowing electrical connection between the two metal substrates. The electrical connection through the spacers 130 may be assisted by welding or brazing through the metal substrates and the spacer. This weld, or braze, also seals the first and second fluid volumes. Further, because electrical interconnection between cells is not reliant on electrical connection between the support structure 131 and the metal substrate 120, the compression load through the support structure (and thus the strength of the support structure) can be reduced in comparison to the interconnect 150 of
For reasons of clarity, there is not shown in
The support structure 131 and conductive support structure 310 are illustrated schematically as corrugated elements, but again other pressed three dimensional features may be used. They may serve to provide electrical connection between adjacent cell units. In doing so, support structures and conductive support structures serve to resist buckling or warping of the metal substrates on either side. The support structures 131 and conductive support structures 310 preferably have gaps (not visible in the cross section shown) for free circulation of fluid through them, left-to-right in the diagram (or right-to-left or front-to-back or back-to-front) and up-to-down in the diagram (or down-to-up or toward and away from the metal substrates), i.e. they are permeable.
In
Two pairs of cell units are shown in each bank 400a,b of
In this way, a parallel-series arrangement of cell units is provided. All anodes of a particular bank are connected in parallel. Likewise, all cathodes of a particular bank are connected in parallel. This assists in meeting current requirements placed upon the stack of cell units. Cell units of one bank are connected in series with cell units of an adjacent bank. The cathodes of a bank (for example, first bank 400a) are connected in series with the anodes of an adjacent bank (for example, second bank 400b). This assists in meeting voltage requirements placed upon the stack. More banks may be added to further increase voltage.
Each bank comprises multiple pairs of cell units. In the illustrated example, there are three pairs of cell units to each bank. However, one, two, or more than three pairs of cell units may also be used. See Table 1 (below).
Two banks, each with three pairs of cell units are shown in
Table 1 shows the increase in volumetric power density relative to the prior art design of
The skilled person will understand that these advantages apply equally to operating the cell units as MS-SOEC units.
The increase in volumetric power density increases for banks having four cells (i.e. two pairs of cell units in a back-to-back or face-to-face arrangement). This is because for a given number of cells in a stack, less isolating layers between banks (which increase stack height) are required.
The gain in volumetric power density is less pronounced on increasing from two pairs of cell units to three pairs of cell units per banks, and so forth. Further, as the number of cell units per bank increases, so does the current produced by a bank. This may be advantageous in high current applications, but leads to greater resistive losses and may require components to be made of thicker, or more conductive, materials to withstand or mitigate resistive heating.
The metal substrate may be entirely flat such that it lies entirely in a single plane, or, as described below, beyond the cell chemistry layers, the substrate may be pressed or formed such that it has 3D features, which features may be created before or after deposition of the cell chemistry.
Spacerless Cell Unit Pair Variants
The next embodiments of
The apexes, or peaks, of the protrusions (or features formed in the substrate) 840 extend away from the second side 126. The metal substrate 120 further comprises a formed feature comprising a flange 850 at its periphery. The flange is orientated in a plane which is parallel to, and vertically separated from (lower, in the orientation shown) than the main plane of the metal substrate 120. The main plane of the metal substrate 120 is that which supports the electrochemically active layers 110. The protrusions 840 and flange 850 are formed in the metal substrate 120 by pressing, stamping, or otherwise forming a planar metal substrate. The porous region and electrochemically active layers 110 may be formed before or after the forming of protrusions 840 and flange 850, but preferably the protrusions 840 and flange 850 are formed before the depositing the electrochemically active layers 110 to reduce the chance of damage to said layers.
The raised port features 910 of adjacent cell pairs interface to space adjacent pairs of cell units and create second fluid volume 430. The height of the raised port features is sufficient to create the second fluid volume, thus also spacing the electrochemically active layer 110 of a cell unit in a first pair of cell units from an electrochemically active layer 110 of a cell unit in a second, adjacent, pair of cell units. The raised port features 910 and ports 980 form a fluid chimney for delivery of fluid to (or exhaust from) the first fluid volume 140.
The planar surface of a raised port feature of a first cell unit interfaces with a corresponding planar surface of a raised port feature of a second cell unit, the second cell unit being in an adjacent pair of cell units to the first cell unit. Thus, in contrast to the previously described cell units, the raised port features 910 obviate the need for gaskets (such as gaskets 180 described with reference to
The interface between the planar surface of a raised port feature of a first cell unit and the corresponding planar surface of a raised port feature of a second cell unit must be sealed in order to seal the chimney, and to prevent mixing of fluids in the first and second fluid volumes. The seal may be made using a gasket: either a preformed gasket or, preferably using a sealing contact paste or liquid that forms an insitu seal. The latter may be disposed in an annular groove in one or both of the interfacing planar surfaces. An (e.g. compressible) annular gasket could additionally be placed—and indeed fixed in position—around the exterior of the raised port features, if desired. Alternatively, and advantageously, the seal may be made by welding a seal around the interfacing planar surfaces of the raised port feature, this further reduces the part count.
Protrusions 1040 are shown as protruding into the first fluid volume 140. They may protrude in alternating manner into and away from that volume. This is described below. Where they protrude away from the fluid volume 140, they protrude to the same level as the raised port features 1050 so as to serve to share stack compression load with the raised port features 1050. Protrusions 840 could alternate likewise.
As is apparent from
An end pair of units of a bank (the pair comprising the non-porous metal sheet 1021 and the cell unit 1020, as per
Method of Assembly (for Spacerless Cell Unit Pair)
By way of example, one preferred method of assembly of a novel arrangement of a spacerless pair of cell units will now be described with reference to
As shown in
Two ports 980a and 980b are shown in the cell unit; the ports are holes through the metal substrate 120. Radially outward from each port is an annular raised port feature 1050 (shown in
The process of cell pair assembly begins with forming of a first cell unit (as described in previous embodiments) by stamping or pressing the metal substrate into shape and forming the port holes peripheral flange 850, protrusions 840 and 1040, and raised port features 1050 (with protrusions 840 protruding on the same side/in the same direction as flange 850 and raised port features 1050 on the opposite side/in the opposite direction).
Porous region 124 and electrochemically active layer 120 may be formed before or after (the latter is preferred) stamping or pressing the metal substrate, by methods described previously with respect to
The port holes may also be referred to as fuel ports because, operated as a MS-SOFC they route fuel (for example, hydrogen gas) to the first fluid volume; operated as a MS-SOEC, they route gas, for example, hydrogen gas (as a product of the MS-SOEC cell units) from the first fluid volume.
A second such cell unit is provided, inverted and placed over the first cell, to form a first pair of cell units in a back-to-back arrangement, as shown in
Once sealed, the inwardly projecting protrusions 1040 around the inner circumference of the annular raised port feature 1050 in the first and second cell units touch each other in an opposite and opposing relationship as seen in the cross-sectional view of
A method of assembly of a cell bank as previously described in any of the previous embodiments follows in the sequence of
As shown in
The process of bank assembly begins with placing a conductive support structure 310 over a first cell pair assembly, contacting the electrochemically active layer 110 to provide for electrical connection to the upper layer of the electrochemically active layer 110. The conductive support structure 310 extends beyond the edge of the metal substrates, at one or more sides thereof and is arranged to not interfere with the chimney formed by the ports and raised port features.
The conductive support structure may be a stamped metal plate, similar to conductive support structure 310 described previously, and it may be in the form of an electrically conducting mesh or similar (as described above with reference to separator 440).
Edge tangs 1510 are also provided, as shown in
Further cell units can be added in the manner described with respect to
The conductive support structures 310 preferably comprise tangs (metal fingers) 311 as shown in
Further steps in a method of cell stack assembly are described with reference to
Cell Unit Pairs Formed by Folding
As shown in
Ports may be formed in substrate 120 between the electrochemically active areas 110 and the fold zone 1620 (and, at the other end of the folded substrate, between the electrochemically active areas 110 and the edge of the substrate) to form a chimney to supply (and/or exhaust) the first (and/or second) fluid volume; the first (second) fluid volume thus being internally manifolded.
The first fluid volume 140 may be sealed at the other end 1630 (i.e. the end distal from the fold zone 1620) using a (e.g. conductive) spacer, such as spacer 130 welded to the metal substrate 120 as further described with respect to
The arrangement of the pair of cell units 1600 forms a repeating unit and may be used in place of the pair of cells 200 in the cell banks described with reference to
As previously described, if used for a solid oxide cell, usually the electrochemically active layer comprises anode layer 113, electrolyte layer 112, and cathode layer 111 deposited over a porous region 124, and an extended electrolyte coating 123 may also be present. The metal substrate (at the same polarity as the innermost electrode) may be connected to an electrical connection (not shown).
The folded pair of cell units 1650 may be substantially similar to the pairs of cell units described with reference to
The pair of cell units 1650 are formed from a metal sheet with formed features which is folded at fold zone 1620. The formed features are made by pressing a planar metal sheet. The formed features comprise protrusions 840 (in the form of dimples) around the chimney, chimney protrusion 910 (which may be annular and used with or without a gasket to seal the chimney), and protrusion 1040 which is outside the chimney. Protrusions 840 and 1040 assist in defining first fluid volume 140 by resisting the stack compression forces. A support structure 131 may be positioned between the porous regions of the substrate 120 to prevent bowing of the substrate 120 to define first fluid volume 140. The electrochemically active layer 110 may be deposited on the porous region 124 of the metal substrate 120 before or after folding the metal sheet.
Support structure 131 may assist in connecting opposed electrodes from adjacent electrochemically active layers 110, but their main role is in defining the first fluid volumes 140. Current collectors 310 collect current form the opposed (outermost) electrodes from adjacent electrochemically active layers 110 and in defining the second fluid volumes 430 (support structures are not shown in first fluid volume but are shown in second fluid volume in
The arrangement of cell units 1700 on a single metal substrate 120 may be provided with spacers 130 or gaskets at the ends to seal first fluid volumes 140 and can be used as a single bank. Multiple banks may be arranged to form stacks of cell units as described previously.
As shown in
The stacks of the folded pairs of cell units are internally manifolded, that is, they have ports within the metal substrates 120 to form an internal manifold(s) or a chimney which connects the first fluid volumes 140 of each pair of cell units.
Number | Date | Country | Kind |
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1915438.4 | Oct 2019 | GB | national |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2020/079783 | 10/22/2020 | WO |