Electrochemical cell device and method for producing an electrochemical cell device
Patent Information
- Application Number
- EP2024799167
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-10-30
- Filing Date
- 2024-10-29
- Publication Date
- 2026-09-09
AI Technical Summary
Existing methods for producing electrochemical cell devices face challenges in efficiently applying functional layers, particularly the electrode layer and electrolyte, without significant deformation or inhomogeneous layer thickness, especially when dealing with recessed metal carriers.
A procedure for producing electrochemical cell devices involves a metal carrier with recesses, where functional layers are applied using a transfer substrate and laminating process, allowing for even layer distribution and minimal deformation, even through large recesses.
This approach enables the production of electrochemical cell devices with smooth, flat, and homogeneously thick functional layers, ensuring high flow rates of process fluids and reducing the risk of layer defects, while maintaining the structural integrity of the metal carrier.
Smart Images
Figure EP2024080512_08052025_PF_FP_ABST
Abstract
Description
[0001] Description
[0002] Electrochemical cell device and method for producing an electrochemical cell device
[0003] State of the art
[0004] A method for producing an electrochemical cell device, in particular an electrochemical half-cell, has already been proposed, wherein in at least one method step a metal carrier of the electrochemical cell device is provided which has at least one recess, and wherein in at least one method step at least one functional layer of the electrochemical cell device is applied to the metal carrier.
[0005] Disclosure of the invention
[0006] The invention is based on a method for producing an electrochemical cell device, in particular an electrochemical half-cell, wherein in at least one method step of the method a metal carrier of the electrochemical cell device is provided which has at least one recess, and wherein in at least one method step of the method at least one functional layer of the electrochemical cell device is applied to the metal carrier.
[0007] It is proposed that, in at least one method step of the method, the at least one functional layer is arranged on the metal carrier in an open state of the recesses. The metal carrier is preferably plate-shaped, in particular cuboid-shaped or cylindrical. The electrochemical cell device preferably has a stacking direction along which the metal carrier and the functional layers are arranged one behind the other or on top of the other. The metal carrier preferably has a stacking surface which runs at least substantially perpendicular to the stacking direction. The stacking surface is preferably at least one of the two largest outer surfaces, in particular the largest outer surface, of the metal carrier. A maximum extension of the metal carrier parallel to the stacking direction is referred to hereinafter as the material thickness of the metal carrier.The material thickness of the metal carrier is preferably smaller than a maximum extension of the metal carrier in any direction perpendicular to the stacking direction. The functional layers are preferably arranged on the stacking surface. The metal carrier preferably has a bottom surface which preferably runs at least substantially parallel to the stacking surface. The at least one recess preferably extends continuously through the metal carrier from the bottom surface to the stacking surface. The metal carrier preferably comprises a plurality of recesses which are in particular structurally identical. The recesses are preferably arranged evenly distributed over the stacking surface and bottom surface. A wall of the metal carrier delimiting the recesses can have a circular, oval, elliptical, angular, in particular rectangular, or other cross-section in a plane perpendicular to the stacking direction.A center line through the recess can run at least substantially parallel to the stacking direction or transversely to the stacking direction, in particular at an angle of at most 45°, preferably of at most 30°, particularly preferably of at most 15°. The recesses are particularly preferably produced by laser drilling or another abrasive process. The metal carrier is preferably made of stainless steel, in particular ferritic stainless steel.
[0008] The term "essentially perpendicular" is intended here to define in particular an orientation of a direction relative to a reference direction, wherein the direction and the reference direction, in particular viewed in a projection plane, enclose an angle of 90° and the angle has a maximum deviation of in particular less than 8°, advantageously less than 5°, and particularly advantageously less than 2°. "Essentially parallel" is intended here to mean in particular an orientation of a direction relative to a reference direction, in particular in a plane, wherein the direction has a deviation from the reference direction of in particular less than 8°, advantageously less than 5°, and particularly advantageously less than 2°.
[0009] The method is preferably intended for producing a fuel cell device, in particular a fuel half-cell or a fuel cell, or an electrolysis cell device, in particular an electrolysis half-cell or an electrolysis cell. The method is particularly preferably intended for producing a solid oxide fuel cell device, in particular a solid oxide fuel half-cell or a solid oxide fuel cell, or a solid oxide electrolysis cell device, in particular a solid oxide electrolysis half-cell or a solid oxide electrolysis cell.Preferably, several functional layers are arranged on the metal carrier, for example at least one protective or barrier layer, at least one electrode layer, at least one electrolyte, optionally a further electrode layer and / or further functional layers known from the prior art, such as in particular a reaction barrier layer, an electron barrier layer or the like. The at least one electrode layer can be constructed in a single layer or in multiple layers, for example, from a functional layer and a conductive layer / current collector layer. The protective or barrier layer is preferably provided to minimize interaction of the metal carrier, in particular the stacking surface, with the electrode layer and / or the environment.
[0010] Preferably, in at least one method step, a raw mass of the at least one functional layer is arranged on the metal carrier, which is cured in a further method step, in particular by sintering. The fact that the at least one functional layer is arranged on the metal carrier should be understood in particular to mean that the functional layer is arranged in a non-cured state on the metal carrier, in particular the stacking surface, or on a further functional layer of the electrochemical cell device already arranged on the metal carrier. The arrangement of a functional layer on the metal carrier can comprise applying a layer that has already been preformed elsewhere to the metal carrier or an initial construction and / or shaping of the functional layer directly on the metal carrier.At the time when the at least one functional layer is built up on the metal carrier, the at least one recess is preferably in an open state. It is conceivable that in a subsequent process step, an additional functional layer, in particular the further electrode layer, is arranged on the metal carrier after the recesses have been closed by the at least one previously applied functional layer. Preferably, at least two, preferably at least three, functional layers are arranged on the metal carrier while the at least one recess is in an open state.
[0011] "Intended" should be understood in particular to mean specifically programmed, designed, and / or equipped. The fact that an object is intended for a specific function should be understood in particular to mean that the object fulfills and / or performs this specific function in at least one application and / or operating state.
[0012] The inventive design allows an electrochemically inactive functional layer, e.g., a protective or barrier layer, to be applied to the cell structure in such a way that, without significant functional impairment, it exerts virtually no negative impact on the permeability of the recess in the metal carrier. Furthermore, the electrode layer and / or the electrolyte can be applied simply and cost-effectively, for example, by a lamination process, even over recesses in the metal carrier that are significantly larger than 10 μm in size, without causing significant penetration of material into the recesses, significant deformation of the electrode layer and / or electrolyte above the recesses, or problems with inhomogeneous layer thicknesses of the electrode layer and / or electrolyte.
[0013] It is further proposed that, in at least one method step of the method, the at least one functional layer and / or a further functional layer, in particular a protective or barrier layer, of the electrochemical cell device is applied and / or built up directly on the metal carrier. Particularly preferably, the at least one functional layer, in particular the protective or barrier layer, is applied directly to the metal carrier, in particular the stacking surface, using a printing process, for example screen printing, or by means of a spraying process, in particular suspension spraying. Alternatively, thermal spraying, a vacuum coating process, for example physical vapor deposition (PVD) or atomic layer deposition (ALD), or another method can be used to apply the protective or barrier layer to the metal carrier.The functional layer applied to the metal carrier, in particular the protective or barrier layer, preferably has at least one recess which is at least substantially the same size as the recess in the metal carrier, in particular the same size apart from a deposition in the edge region of the recess in the metal carrier, for example due to printing paste flowing in at the edge of the recess in the metal carrier. In particular, an opening width of the at least one recess in the metal carrier after application of the protective or barrier layer is at least 50%, preferably more than 75%, of the opening width of the at least one recess before application of the protective or barrier layer. The recess can already arise during the application of the protective or barrier layer and / or be formed or enlarged after application.Thanks to the inventive design, the closure of the recess in the metal carrier by the at least one functional layer can be advantageously kept to a minimum. In particular, the permeability of the functional layer for a process fluid to the electrode layer can be advantageously kept high. In particular, the number of recesses can be advantageously kept small to ensure a sufficient supply of the process fluid to the electrode layer.
[0014] It is further proposed that, in at least one method step of the method, the functional layer and / or further functional layer at least partially applied to the metal carrier is subjected to a pressure difference directed through the at least one recess. Particularly preferably, an overpressure, in particular relative to the functional layer and / or the surroundings, is created on a side of the metal carrier formed by the base surface. Alternatively, a negative pressure is generated on a side of the metal carrier on which the functional layer is arranged, in particular relative to the base surface and / or the surroundings.The pressure difference is intended to pull or push a part of the functional layer or functional layer material of the functional layer that projects beyond the edge of the recess and has at least partially taken up a volume of the recess in the metal carrier out of the recess or into the recess. The pressure difference can be applied during application, at a time overlapping with application, or after application of the functional layer, in particular at least before the functional layer has hardened. The pressure difference is preferably at least 10 mbar, preferably at least 25 mbar, particularly preferably at least 50 mbar. The pressure difference is preferably at most 10 bar, preferably at most 5 bar, particularly preferably at most 1 bar.Due to the design according to the invention, a layer thickness of the functional layer which has run into the recess can be advantageously kept low along the inner walls of the recess and thus an influence on the permeability of the recess can be advantageously kept low.
[0015] It is further proposed that in at least one method step of the method, the at least one functional layer and / or a further functional layer of the electrochemical cell device is transferred to the metal carrier by means of a transfer substrate. Preferably, the at least one further functional layer is transferred to the functional layer already arranged on the metal carrier. Preferably, the at least one functional layer is built up and / or formed on the transfer substrate, for example by means of screen printing or another suitable method, such as another printing process such as gravure or flexographic printing, by means of suspension spraying, casting or doctor blade processes or other methods known from the prior art. Preferably, several further functional layers are transferred, in particular together, to the metal carrier with the transfer substrate.Preferably, at least one additional functional layer is built up and / or formed on the further functional layer, in particular by means of screen printing or the like. The transfer substrate is preferably smooth, alternatively structured. The transfer substrate is, for example, a plastic film, a coated paper or the like. The at least one further functional layer is preferably transferred to the metal carrier, in particular with the protective or barrier layer, with the at least one recess in an open state, and preferably laminated on. During lamination, the at least one further functional layer is bonded to the metal carrier or the protective or barrier layer applied thereto under the action of a force and, if appropriate, additionally a temperature. After lamination has been completed, the transfer substrate is removed from the at least one additional functional layer.The inventive design advantageously allows for the creation of smooth and advantageously flat functional layers with advantageously homogeneous layer thicknesses. In particular, the risk of defects forming in the layers, such as sagging or fluctuating thicknesses of the functional layers above recesses in the substrate, as well as any resulting defects during sintering of the layers, such as the formation of cracks, pores, or cavities, can be advantageously minimized.
[0016] It is further proposed that at least one electrode layer, in particular the one already mentioned, be printed onto the transfer substrate as a functional layer and / or a further functional layer. The electrode layer is preferably printed onto the electrolyte previously applied to the transfer substrate. Preferably, the electrode layer is transferred, together with the electrolyte, to the metal carrier with the protective or barrier layer in a single process step. The inventive design makes it possible to achieve an advantageously smooth and advantageously flat electrode-electrolyte composite.
[0017] It is further proposed that at least one electrolyte, in particular the one already mentioned, is printed as a functional layer and / or further functional layer onto the transfer substrate. The electrolyte is preferably printed directly onto the transfer substrate. In an embodiment with the further electrode layer, the further electrode layer is alternatively printed onto the transfer substrate and the electrolyte onto the further electrode layer and, in particular in a third step, the electrode layer is printed onto the electrolyte on the further electrode layer. The embodiment according to the invention, ie when the electrolyte is printed directly onto the transfer substrate, makes it possible to achieve an advantageously smooth and advantageously flat electrolyte.
[0018] It is further proposed that several functional layers of the electrochemical cell device be laminated together onto the metal carrier. Lamination preferably comprises subjecting the unit composed of adjacent metal carriers and functional layers, in particular including the transfer substrate, to pressure and / or temperature. The unit composed of adjacent metal carriers and functional layers preferably comprises at least the protective or barrier layer, the electrode layer, and the electrolyte, and in particular the further electrode layer. Lamination can be carried out in a batch process, for example by means of a heating press, or in a continuous process, in particular by means of a calender or the like. After lamination, the transfer substrate is preferably separated from the at least one further functional layer, in particular the electrolyte.Due to the design according to the invention, the electrochemical cell device can be manufactured in advantageously few individual steps.
[0019] It is further proposed that in at least one method step of the method the at least one recess is made in the metal carrier with an opening width of at least 10 pm. The opening width is preferably at least 25 pm. Preferably the opening width is up to 200 pm, in particular up to 100 pm, especially up to 50 pm. The at least one recess can be produced, for example, by drilling, laser drilling, etching or other methods known from the prior art. The opening width is preferably measured in a plane perpendicular to the stacking direction, in particular in a plane in which the stacking surface is arranged. The opening width is preferably the smallest distance between opposite wall sections of the metal carrier which delimit the at least one recess.The inventive design allows for an advantageously high flow rate of a process fluid through the recess into the electrode layer. Furthermore, the process for producing the recess can be advantageously designed to be efficient; in particular, the number of recesses to be produced can be advantageously kept small. Furthermore, the risk or extent of the recess becoming blocked by the barrier or protective layer can advantageously be kept low.
[0020] Furthermore, an electrochemical cell device produced by a method according to the invention is proposed. The electrochemical cell device preferably comprises the metal carrier with the at least one recess. The electrochemical cell device preferably comprises the protective or barrier layer as a functional layer arranged on the metal carrier. The electrochemical cell device preferably comprises the electrode layer as a further functional layer arranged on the protective or barrier layer. The electrochemical cell device preferably comprises the electrolyte as an additional further functional layer arranged on the electrode layer. In some embodiments, the electrochemical cell device comprises the further electrode layer arranged on the electrolyte.The electrochemical cell device can further comprise at least one reaction barrier layer and / or one electron barrier layer. The electrode layer and / or the further electrode layer can each be formed as a single layer or multiple layers. The inventive design makes it possible to provide an electrochemical cell device with advantageously smooth and flat functional layers with advantageously homogeneous layer thicknesses, which are simultaneously advantageously accessible to process fluids.
[0021] It is further proposed that the electrochemical cell device comprise a protective or barrier layer, in particular the one already mentioned, as a functional layer, which has at least one barrier recess which is at least substantially the same size as the recess in the metal carrier. Substantially the same size is preferably understood to mean with a deviation of less than 50%, preferably less than 25%, particularly preferably less than 10% relative to one another. In particular, the barrier recess is smaller than or the same size as the recess in the metal carrier. Preferably, the barrier recess and the recess in the metal carrier are arranged concentrically to one another, in particular at least within the scope of the manufacturing accuracy, in particular with respect to an axis that is at least substantially parallel to the stacking direction.Preferably, the protective or barrier layer has a barrier recess at least substantially equal in size to the corresponding recess in the metal carrier at at least the majority of the, in particular each, recess(es) in the metal carrier. It is conceivable for the protective or barrier layer to have projections that extend into the protective or barrier recess and / or the recess in the metal carrier. The inventive design allows for an advantageously high flow rate of process fluids through the protective or barrier layer.
[0022] The method according to the invention and / or the electrochemical cell device according to the invention are not intended to be limited to the application and embodiment described above. In particular, the method according to the invention and / or the electrochemical cell device according to the invention may comprise a number of individual elements, components, units, and method steps that differs from the number stated herein to fulfill a functionality described herein. Furthermore, in the value ranges specified in this disclosure, values within the stated limits are also to be considered disclosed and can be used arbitrarily.
[0023] Drawings
[0024] Further advantages will become apparent from the following description of the drawings. The drawings illustrate an exemplary embodiment of the invention. The drawings, the description, and the claims contain numerous features in combination. Those skilled in the art will also expediently consider the features individually and combine them into useful further combinations.
[0025] They show:
[0026] Fig. 1 is a schematic representation of an electrochemical cell device according to the invention and
[0027] Fig. 2 is a schematic flow diagram of the method according to the invention.
[0028] Description of the embodiment
[0029] Figure 1 shows an electrochemical cell device 12. The electrochemical cell device 12 preferably comprises a metal carrier 14. The electrochemical cell device 12 preferably comprises a plurality of functional layers 18, 20, 22, 24 arranged on the metal carrier 14. The functional layers 18, 20, 22, 24 are preferably arranged along a stacking direction 40. The metal carrier 14 preferably comprises a stacking surface 42 on which the functional layers 18, 20, 22, 24 are arranged. The stacking surface 42 preferably extends at least substantially parallel to the stacking direction 40. The electrochemical cell device 12 preferably comprises a protective or barrier layer 26 as the functional layer 18. The electrochemical cell device 12 preferably comprises an electrode layer 28 as the functional layer 20. The electrochemical cell device 12 preferably comprises an electrolyte 32 as the functional layer 22.In some embodiments, the electrochemical cell device 12 optionally comprises a further electrode layer 30 as a functional layer 24. Along the stacking direction 40, the electrochemical cell device 12 preferably has the following sequence of layers: metal carrier 14, protective or barrier layer 26, electrode layer 28 and electrolyte 32 and optionally a further electrode layer 30. For the sake of simplicity, it is assumed hereinafter that the electrochemical cell device 12 is designed as a solid oxide fuel half-cell (without the further electrode layer 30). The electrode layer 28 is designed, for example, as a fuel electrode and is intended in particular for operation as an anode. The electrode layer 28a comprises, for example, cerium gadolinium oxide (CGO) and nickel oxide (NiO). The electrolyte 32 and / or the protective or barrier layer 26 comprises, for example, CGO.
[0030] The metal carrier 14 preferably comprises at least one bottom surface 44, which preferably runs at least substantially parallel to the stacking surface 42. The metal carrier 14 preferably comprises at least one recess 16. The recess 16 preferably extends from the bottom surface 44 to the stacking surface 42 through the metal carrier 14. The recess 16 preferably has an opening width 36 in a plane perpendicular to the stacking direction 40. In a particularly advantageous embodiment, the opening width 36 is preferably up to 200 μm, preferably between 10 μm and 100 μm, particularly preferably between 25 μm and 50 μm. Depending on the application, smaller opening widths 36 can also be realized. The protective or barrier layer 26 has a barrier recess 38. The barrier recess 38 is preferably arranged concentrically with the recess 16.The barrier recess 38 is at least substantially the same size as the recess 16 of the metal carrier 14. Preferably, a barrier opening width 46 of the barrier recess 38 perpendicular to the stacking direction 40 is at least substantially the same size as the opening width 36 of the recess 16 of the metal carrier 14. The barrier opening width 46 is preferably smaller than or equal to the opening width 36 of the recess 16 of the metal carrier 14. In some embodiments, the protective or barrier layer 26 protrudes into the recess 16 of the metal carrier 14. In particular, an inner wall of the metal carrier 14, which delimits the recess 16, is at least partially coated with the protective or barrier layer 26.
[0031] Figure 2 shows a method 10 for producing the electrochemical cell device 12. Figure 2 shows a plurality of preliminary stages of the electrochemical cell device 12, wherein, for the sake of clarity, each component has been provided with a reference numeral only once. In at least one method step of the method 10, a metal carrier 14 of the electrochemical cell device 12 is provided. The method 10 comprises a metal carrier processing 48. In the metal carrier processing 48, the at least one recess 16 is made in the metal carrier 14, e.g. by drilling, laser drilling, etching or another suitable method. The at least one recess 16 is made in the metal carrier 14 with the opening width 36. Optionally, in the metal carrier processing 48, in particular after the at least one recess 16 has been made, the metal carrier 14 is subjected to a temperature treatment.
[0032] The method 10 preferably comprises an application step 50. In the application step 50, the protective or barrier layer 26 is applied and / or built up directly on the metal carrier 14, in particular the stacking surface 42, preferably by means of a printing process or a spraying process. The at least one recess 16 is in an open state at least before the application step 50. The at least one recess 16 can be completely covered by the application step 50 or can remain at least partially open. Depending in particular on the opening width 36, the recess 16 is at least partially filled, for example, with printing paste or suspension flowing into the recess 16. The method 10 preferably comprises a pressurization 52.During pressurization 52, the protective or barrier layer 26 at least partially applied to the metal carrier 14 is subjected to a pressure difference which is directed through the at least one recess 16. The pressurization 52 is provided to suck the suspension or printing paste for producing the protective or barrier layer 26 along a wall of the metal carrier 14 out of the at least one recess 16 or deeper into the at least one recess 16. A layer thickness of the protective or barrier layer 26 which has run into the at least one recess 16 is thus reduced and an influence of the protective or barrier layer 26 on the permeability of the recess 16 is reduced. After the application step 50 or after pressurization 52, the at least one recess 16 is still or again in an open state.
[0033] In a further method step, a transfer substrate 34, in particular a smooth and / or flat one, is preferably provided. In a further application step 54 of the method 10, the electrolyte 32 is printed onto the transfer substrate 34, for example, by screen printing. In an additional application step 56 of the method 10, the electrode layer 28 is printed onto the electrolyte 32 located on the transfer substrate 34, for example, by screen printing. After the additional application step 56, the transfer substrate 34, the electrolyte 32, and the electrode layer 28 form a transfer unit.
[0034] In a joining step 58 of the method 10, the additional functional layers 20, 22 of the electrochemical cell device 12 are transferred to the metal carrier 14 by means of the transfer substrate 34. The transfer unit is preferably arranged on the metal carrier 14. In the joining step 58, the transfer unit is preferably arranged with the electrode layer 28 first on the protective or barrier layer 26 arranged on the metal carrier 14.
[0035] In a lamination step 60, the additional functional layers 20, 22 of the electrochemical cell device 12 are laminated together onto the metal carrier 14 with the protective or barrier layer 26. This allows the additional functional layers 20, 22 to be transferred to the metal carrier 14 without significant deformation of the layers, such as severe sagging / indentation into the at least one recess 16 of the metal carrier 14. The carrier film is preferably detached from the electrolyte 32 following the lamination step 60 and disposed of or reused.
[0036] Preferably, the unit comprising the metal carrier 14 and the functional layers 18, 20, 22 is subjected to a thermal treatment, particularly following the lamination step 60, in particular to burn out organic components of the printing pastes or suspension of the functional layers 18, 20, 22. Preferably, the unit comprising the metal carrier 14 and the functional layers 18, 20, 22 is sintered, particularly following the thermal treatment.
Claims
Claims 1 . Method (10) for producing an electrochemical cell device (12), in particular a half-cell, wherein in at least one method step a metal carrier (14) of the electrochemical cell device (12) is provided, which has at least one recess (16), and wherein in at least one method step at least one functional layer (18, 20, 22, 24) of the electrochemical cell device (12) is applied to the metal carrier (14), characterized in that in at least one method step the at least one functional layer (18, 20, 22) is arranged on the metal carrier (14) in an open state of the at least one recess (16).
2. Method (10) according to claim 1, characterized in that in at least one method step the at least one functional layer (18) and / or a further functional layer (20, 22, 24), in particular a protective or barrier layer (26), of the electrochemical cell device (12) is applied and / or built up directly on the metal carrier (14). • 3. Method (10) according to claim 2, characterized in that in at least one method step, the functional layer (18) and / or further functional layer (20, 22, 24) at least partially applied to the metal carrier (14) is subjected to a pressure difference which is directed through the at least one recess (16).
4. Method (10) according to one of the preceding claims, characterized in that in at least one method step the at least one functional layer (18) and / or a further functional layer (20, 22, 24) of the electrochemical cell device (12) is transferred to the metal carrier (14) by means of a transfer substrate (34).
5. Method (10) according to claim 4, characterized in that at least one electrode layer (28, 30) is printed as a functional layer (18) and / or further functional layer (20, 22, 24) on the transfer substrate (34).
6. Method (10) according to claim 4 or 5, characterized in that at least one electrolyte (32) is printed as a functional layer (18) and / or further functional layer (20, 22, 24) onto the transfer substrate (34).
7. Method (10) according to one of the preceding claims, characterized in that several functional layers (20, 22, 24) of the electrochemical cell device (12) are laminated together onto the metal carrier (14).
8. Method (10) according to one of the preceding claims, characterized in that in at least one method step the at least one recess (16) with an opening width (36) of at least 10 pm is introduced into the metal carrier (14).
9. An electrochemical cell device (12) manufactured by a method (10) according to any one of the preceding claims.
10. Electrochemical cell device (12) according to claim 9, with at least one protective or barrier layer (26) as functional layer (18), which has at least one barrier recess (38) which is at least substantially the same size as the recess (16) of the metal carrier