CN118119737A - Electrochemical cell and frame for stacked device - Google Patents
Electrochemical cell and frame for stacked device Download PDFInfo
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- CN118119737A CN118119737A CN202280069261.1A CN202280069261A CN118119737A CN 118119737 A CN118119737 A CN 118119737A CN 202280069261 A CN202280069261 A CN 202280069261A CN 118119737 A CN118119737 A CN 118119737A
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to a novel frame for electrochemical cells and stacked devices. The present invention relates to a frame, an electrochemical cell, a pre-assembled module and a stacked device comprising a frame according to the invention, and to a method for producing a pre-assembled module, an electrochemical cell and a stacked device comprising a frame according to the invention. The frame, electrochemical cell and stacked device according to the invention are suitable for converting or generating gases and liquids under pressure. The invention is based on a novel framework and sealing concept. The invention also relates to a cover for a stacked device.
Description
The present invention relates to a frame for electrochemical cells and stacked devices for electrochemical conversion or generation of gases and liquids under pressure. The present invention relates to a novel frame for electrochemical cells, stacked devices and preassembled modules, comprising a frame according to the invention, a method of manufacturing a preassembled module and a method of manufacturing a stacked device. The frame according to the invention, the electrochemical cell according to the invention and the stacked device according to the invention are suitable for electrochemical conversion under pressure or for the generation of gases and liquids, such as electrolysis cells, fuel cells or electrochemical compression cells. The invention is based on a new frame and sealing concept. The invention also relates to a cover for a stacked device.
The electrochemical cell is capable of generating electrical energy by converting a substance or forming other substances by energizing. The electrochemical cell has at least two electrodes as electron conductors and an electrolyte as ion conductor. The preferred electrolyte for the cells developed herein is a solid electrolyte such as an ion conducting membrane.
Conventional solid electrolyte electrochemical cells consist of an ion-conducting membrane, possibly coated with a catalyst, on which the reaction takes place. On the anode and cathode sides, porous electrodes (anode and cathode) transport gas or liquid toward or away from the electrolyte. Frames made of conventional metal or high strength Plastic (PEEK) ensure the inflow or outflow of gases and liquids under pressure. The electrode (anode or cathode) is inserted into the frame. The frame sides are sealed by O-rings or other seals (e.g., flat gaskets or injection molded seals) to prevent gas or liquid from escaping from the electrochemical cell. To increase the yield, electrochemical cells may be connected in series to form a cell stack. The individual electrochemical cells are separated by so-called bipolar plates. Such a device is referred to as a stacked device 23.
Electrochemical cells and stacked devices comprising a frame are known in the art.
EP 3 699 323 A1 relates to the electrode supply of an electrode stack (for example an electrolysis cell).
DE 25 33 728 A1 relates to an electrolysis cell having bipolar electrodes arranged side by side and an outer frame enclosing at least one chamber of the electrolysis cell.
EP 3,770,303 A1 relates to an electrode packing unit for a stacked structure of an electrochemical reactor, which unit has a bipolar plate, two electrode plates and two current-carrying structures between the bipolar plate and the electrode plates.
Operating a conventional electrochemical cell under pressure typically encounters the following difficulties:
1. seal tightness problems in cell stacks (i.e., stacked devices), the frames of many electrochemical cells are stacked on top of each other, and each material used in the frames and other components has manufacturing tolerances. This may use O-rings or other seals that may not have sufficient contact pressure at certain locations on the frame. It is difficult or impossible to achieve a tight seal with known seals, especially when the gas or liquid is under pressure.
2. Mechanical stability of the frame: when the gas and liquid are converted or generated under pressure, the plastic frame will deform (fig. 2).
3. A small gap 17 is left between the electrode and the frame 1. During differential pressure operation, a solid electrolyte (e.g., membrane 13) is pressed into gap 17. The solid electrolyte (e.g., membrane 13) is pressed or climbed 24 into the gap 17. This effect is exacerbated if the frame 1 is deformed due to low mechanical stability (see point 2), making the gap 17 larger (fig. 2).
4. The frame typically includes channels for liquid and gas supply and discharge. In the prior art, it is common to mill channels in frames, i.e. in metal or plastic parts, which is costly.
In order to be able to produce gases or liquids for industrial purposes at high pressure by means of an electrochemical cell, or to be able to introduce gases or liquids into an electrochemical cell at high pressure, there is a need for an improved electrochemical cell which can be operated at high pressure without the above-mentioned drawbacks.
The present invention solves this problem by the claims 1 to 21.
The object of the invention is a frame 1 for an electrochemical cell 2 of a stacked device 23, the frame 1 comprising a first side 4 of the frame, a second side 5 of the frame, an anode frame 8 and a cathode frame 11, the first side 4 of the frame having a planar first surface, the second side 5 of the frame being opposite the first side 4 and having a planar second surface, and
Wherein the anode frame comprises a first side 4 of the frame, a side 4 "opposite the first side 4 of the frame of the anode frame, and a first opening 6 for receiving an anode 7, wherein the first opening 6 extends from the first side 4 of the frame to the side 4" of the anode frame opposite the first side 4 of the frame,
Wherein the cathode frame 11 comprises a second side 5 of the frame, a side 5 "opposite the second side 5 of the frame of the cathode frame, and a second opening 9 for receiving the cathode 10, wherein the second opening 9 extends from the second side 5 of the frame to the side 5" of the cathode frame opposite the second side 5 of the frame, wherein the side 4 "opposite the first side 4" of the frame of the anode frame and the side 5 "opposite the second side 5 of the frame of the cathode frame are arranged adjacent,
Wherein the anode frame 8 and the cathode frame 11 are connected to each other,
Wherein the first opening 6 and the second opening 9 are connected to each other,
Wherein the first opening 6 is larger than the second opening 9, wherein the anode frame 8 and the cathode frame 11 are arranged such that a side 4 "opposite to the first side 4 of the frame of the anode frame and a side 5" opposite to the second side 5 of the frame of the cathode frame form a step 12 at the transition from the anode frame 8 to the cathode frame 11.
In the frame 1 of the present invention, the step 12 is preferably a part of the cathode frame 11. In the frame 1 of the invention, the step 12 is preferably adjacent to the second opening 9. In the frame 1 of the present invention, the step 12 preferably frames the second opening 9. In the frame 1 according to the invention, the step 12 preferably forms a planar third surface, which acts as a support surface for the solid electrolyte, for example the membrane 13. In the frame 1 according to the invention, the step 12 is preferably part of the cathode frame 11 and forms a planar third surface which acts as a support surface for the solid electrolyte, for example the membrane 13. In the frame 1 according to the invention, the step 12 is preferably part of the cathode frame 11, adjacent to the second opening 9, framing the second opening 9 and forming a planar third surface, which acts as a support surface for the solid electrolyte, for example the membrane 13.
According to the invention, an ion-conducting membrane is preferably used for the membrane 13.
The anode frame 8 includes a core 21 and a sealing material coating layer 22. The anode frame 8 preferably comprises a core 21 made of metal or other suitable material, wherein the core 21 is coated with a coating 22 of sealing material. The core 21 of the anode frame 8 is entirely or partially coated with a sealing material coating 22. The cathode frame 11 includes a core 21 and a sealing material coating layer 22. The cathode frame 11 preferably includes a core 21, the core 21 preferably being made of metal or other suitable material, and the core 21 being coated with a coating 22 of sealing material. The core 21 of the cathode frame 11 is entirely or partially coated with a sealing material coating 22. Any sealing material may be used as the sealing material coating 22, such as rubber, in particular Ethylene Propylene Diene Monomer (EPDM). For example, the sealing material coating 22 may include or consist of ethylene propylene diene monomer. The sealing material coating 22 is preferably a seal or sealing function in the electrochemical cell 2 or in the stacked device 23. The subject of the invention is a frame 1 for an electrochemical cell 2, having a core 21, the core 21 preferably being made of metal, wherein the core 21 is coated with a sealing material, preferably rubber, such as EPDM (fig. 3a and 3 b). The core 21 of the anode frame 8 is entirely or partly coated with a coating 22 of sealing material, in particular a seal. The core 21 of the cathode frame 11 is entirely or partially coated with a coating 22 of sealing material, in particular a seal. Any sealing material may be used as the seal, such as rubber, in particular ethylene propylene rubber (EPDM). For example, the seal may comprise or consist of ethylene propylene diene monomer.
The core 21 of the anode frame 8 preferably comprises or consists of metal. The core 21 of the cathode frame 11 preferably comprises or consists of metal. The core 21 made of metal has good mechanical stability. In addition, other materials having similar mechanical properties may also be used as the material of the core 21. Such as high strength Plastics (PEEK), polytetrafluoroethylene (PTFE), in particular reinforced PTFE or molecularly reinforced PTFE. The coating 22 made of a sealing material, preferably rubber, such as Ethylene Propylene Diene Monomer (EPDM), may create a sealing effect, i.e. the sealing material acts as a seal.
In a preferred embodiment, the entire surface of the core 21 of the anode frame 8 is coated with a sealing material coating 22. In a further preferred embodiment, at least 90%, preferably at least 95% or more of the surface of the core 21 of the anode frame 8 is coated with a sealing material coating 22. In a preferred embodiment, the entire surface of the core 21 of the cathode frame 11 is coated with a sealing material coating 22. In a more preferred embodiment, at least 90%, preferably at least 95% or more of the surface of the core 21 of the cathode frame 11 is coated with the sealing material coating 22. In these embodiments, the sealing surface is very large.
In an alternative embodiment, less than 90% of the surface of the core 21 of the anode frame 8 is coated with the sealing material coating 22. In further alternative embodiments, less than 90% of the surface of the core 21 of the cathode frame 11 is coated with the sealing material coating 22. However, in these alternative embodiments, the surface area of the core 21 of the anode frame 8 and/or the core 21 of the cathode frame 11 is coated with a sealing material coating 22, which is necessary to achieve a complete sealing of the electrolysis cell 2. Preferably, in these alternative embodiments, the surface area of the core 21 of the anode frame 8 and/or the core 21 of the cathode frame 11 surrounding the first opening 6 and/or the second opening 9 is at least coated with a sealing material coating 22. For example, the area of the surface of the core 21 of the anode frame 8 is from 0.5cm to 2.5cm, preferably 1cm to 2cm, for example 1.5cm, which directly surrounds the first opening 6. For example, the surface of the core 21 of the cathode frame 11 has an area of from 0.5cm to 2.5cm, preferably from 1cm to 2cm, for example 1.5cm, which directly surrounds the second opening 9.
The metal has good mechanical stability, while the coating 22 made of a sealing material, preferably rubber, such as EPDM, has a sealing effect. The surface of the core 21 made of metal of the anode frame 8 is preferably all or at least 90%, for example at least 95% or more, or the surface of the core 21 made of metal of the cathode frame 11 is preferably all or at least 90%, for example at least 95% or more, coated with a sealing material, preferably rubber, for example EPDM, which means that the sealing surface is very large.
For example, a further advantage of a stable core 21 made of metal and a coating 22 made of sealing material is that the components of anode 7 and cathode 10, etc., can be pressed into frame 1, in particular into anode frame 8 and cathode frame 11 (press fit). This prevents the frame 1 or the stacked device 23 in the electrochemical cell 2 from being deformed when performing substance conversion power generation or substance conversion using electric power under high pressure or pressure difference (for example, electrolysis performed under a pressure difference of up to 40 bar). A larger gap 17 is formed between the individual components within the frame 1 within the electrochemical cell 2 or within the frame 1 contained in the stacked arrangement 23, and between the individual components and the frame 1 or the frame 1. For example, no large gap 17 is formed between the cathode 10 and the frame 1 and/or between the anode 7 and the frame 1 (fig. 8).
The metal used for the core 21 of the anode frame 8 and/or the cathode frame 11 may be stainless steel, for example stainless steel having a thickness of 0.01 to 1mm, preferably 0.5 mm. The thickness of the coated core 21 of the anode frame 8, i.e. the core 21 and the sealing material 22 coating, and/or the coated core 21 of the cathode frame 11, i.e. the core 21 and the sealing material coating 22, may be 1 to 5mm, preferably 2 to 3mm, e.g. 2.2mm. Materials with similar properties, such as highly reinforced plastics, e.g. PTFE, molecularly reinforced PTFE, are also suitable for the core 21.
The coating 22 made of the sealing material has a thickness. The thickness of the sealing material coating 22 is 1 to 4.5mm, for example 2 to 3mm. Preferably, the thickness of the sealing material coating 22 around the core 21 of the anode frame 8 is the same throughout. The thickness of the sealing material coating layer 22 around the core 21 of the cathode frame 11 is preferably the same everywhere. In a particular embodiment, the core 21 of the anode frame 8 has areas where the layer thickness of the sealing material coating 22″ is reduced compared to the layer thickness of the sealing material coating 22 (fig. 10b to 10d, fig. 14, fig. 16 and 17). In a particular embodiment, the core 21 of the cathode frame 11 has areas where the layer thickness of the sealing material coating 22 "is reduced compared to the layer thickness of the sealing material coating 22. For example, the coating thickness of the sealing material coating 22″ is reduced by 1mm compared to the coating thickness of the sealing material coating 22. For example, the thickness of the sealing material coating 22 is 4mm, and the thickness of the sealing material coating 22″ is 3mm after being reduced. For example, the layer thickness of the sealing material coating layer 22 is 10mm or less, preferably 5mm, 3mm, 2mm or 1.5mm, 1mm or less. For example, the reduced thickness of the sealing material coating 22 is 9mm or less, preferably 4mm, 2.8mm, 1.9mm or less 1.45mm, 0.95mm or less. For example, the difference between the layer thickness of the sealing material coating 22 and the reduced layer thickness of the sealing material coating 22″ is 1mm, 0.7mm, 0.5mm or less, such as 0.3mm, 0.2mm, 0.1mm, 0.05mm or less.
For example, the first opening 6 is at least 0.5mm or 1mm larger than the second opening 9, for example 2mm or more, 0.5cm, preferably 1cm, particularly preferably 1.5cm or more. The step 12 formed by the larger first opening 6 and the smaller second opening 9 in the cathode frame 11 is preferably of the same width everywhere (fig. 7 b). Or the steps 12 may have different widths at different points. The width of the step 12 and the width of the planar third surface for accommodating the solid electrolyte (e.g., the membrane 13) may be the same or may have different widths at different points.
For example, the outer dimensions of the anode frame 8 may be 20-70cm by 20-70cm, such as 50cm by 50cm or 35cm by 35cm. The first opening 6 may be 11-51cm x 11-51cm, for example 21cm x 21cm or 15cm x 15cm in size (fig. 9 b). The outer dimensions of the cathode frame 11 may be 20-70cm x 20-70cm, such as 50cm x 50cm or 35cm x 35cm. The dimensions of the second opening 9 may be 10-50cm x 10-50cm, for example 20cm x 20cm or 14cm x 14cm (fig. 9 a). The outer dimensions of the anode frame 8 and the cathode frame 11 are preferably the same. The dimensions of the first opening 6 and the second opening 9 are chosen such that the first opening 9 is larger than the second opening 9, such that a step 12 is formed when the anode frame 8 and the cathode frame 1 interact as a frame 1.
The skilled person can design the frame 1, the anode frame 8 and the cathode frame 11 in various shapes, such as square, rectangular and circular. Since the shape of the frame 1 can be freely selected, the contact pressure in certain areas of the frame 1 can be adjusted by increasing or decreasing the thickness of the frame, preferably by decreasing the thickness of the sealing material coating 22. The thickness of the sealing material coating 22 may be increased. This allows to create areas of thicker layer thickness of the coating in certain areas on the core 21 than other areas of the anode frame 8 or cathode frame 11. The thickness of the sealing material coating 22 can be reduced. Thus, it is possible to create a region in which the layer thickness of the sealing material coating 22 on the core 21 is thinner than other regions of the anode frame 8 or the cathode frame 11. According to the invention, areas of different layer thickness of the sealing material coating 22 can assume different functions in the frame 1.
To avoid lateral leakage, the pressure in the active area may be increased by adding an annular protrusion 26 "(e.g., adding an annular rubber layer) to the layer thickness of the sealing material coating 22. For example, the width of the annular projection 26″ of the thickness of the sealing material coating 22 may be 1mm. The difference in layer thickness between the sealing material coating 22 and the annular protrusion 26 "may be 1mm, 0.5mm, 0.1mm, 0.05mm, etc.
The subject of the invention is a frame 1 in which the sealing material coating 22 "of certain areas of the anode frame 8 and/or of the cathode frame 11 is reduced compared to the layer thickness of the sealing material coating 22, for example, in order to reduce the contact pressure.
The subject of the invention is a frame 1 in which the anode frame 8 has an annular projection 26 "surrounding the first opening 6 in certain areas by a coating 22 of sealing material, for example in order to increase the sealing effect. The subject of the invention is a frame 1 in which the sealing material coating 22 has an annular projection 26″ surrounding the second opening 9 in certain areas of the cathode frame 11, for example in order to increase the sealing effect.
In the square anode frame 8, the first opening 6 may be formed by a first side 27, a second side 28, a third side 29 and a fourth side 30. In a square cathode frame 11, the second opening 9 may be formed by a first side 27", a second side 28", a third side 29 "and a fourth side 30".
The electrochemical cell 2 or other components of the stacked apparatus 23 can be saved by installing these components as structures in the frame 1, the anode frame 8 and the cathode frame 11, in particular the core 21 of the anode frame 8 and the cathode frame 11 is coated with the sealing material coating 22. For example, the coating 22 made of sealing material may be a coating made of rubber, comprising a rubber lip 25, e.g. the rubber lip 25 is arranged at the connection area for a single voltage measurement. Thus, insulating foil can be saved. In the frame 1 according to the present invention, the sealing material coating layer 22 of the anode frame 8 and/or the sealing material coating layer 2 of the cathode frame 11 have other functions in addition to the sealing function. For this purpose, the sealing material coating 22 of the anode frame 8 and/or the cathode frame 11 comprises a corresponding embodiment, for example a rubber lip 25.
Other desired components may be manufactured directly from the sealing material coating 22, thereby reducing the number of individual components required to manufacture the electrochemical cell 2 or the stacked apparatus 23. This greatly reduces the effort required to assemble the stacked apparatus 23. Also, the insertion of means for connecting the anode frame 8 and the cathode frame 11, such as pins 19 and holes 18, in the anode frame 8 and/or the cathode frame 11 eliminates the need for additional assembly aids.
In a preferred embodiment, the sealant coating 22 includes one or more type II channels 15. The type II channel 15 is designed as a region in the sealing material coating 22, in which region the layer thickness of the sealing material coating 22″ is reduced compared to the layer thickness of the sealing material coating 22. Thus, the type II channel 15 is a depression or concave unit on the sealing material coating 22, which does not contribute to the sealing effect. Adjacent single II-channels 15 are separated by projections 26. For example, the projection 26 between two adjacent type II channels 15 is a region in which the layer thickness of the sealing material coating 22 of the core 21 is not reduced. In the region where the single type II channel 15 is arranged, the reduced layer thickness of the sealing material coating 22 "may be chosen independently of the reduced layer thickness made of the sealing material 22" in other regions of the coating surrounding the core 21, which other regions may also have a reduced layer thickness of the coating made of the sealing material. In particular embodiments, the core 21 is devoid of the sealant coating 22 in one or more regions representing one or more of the type II channels 15.
In a preferred embodiment, the first opening 6 framed by the anode frame 8 and the second opening 9 framed by the cathode frame 11 are of different sizes (fig. 7b, 8, 9a and 9 b). For example, the cathode frame 11 is smaller and the anode frame 8 is larger. This means that at a pressure difference, for example of 40 bar, i.e. when only the cathode side of the electrochemical cell 2 is operated under pressure, or only the cathode side of the stacked arrangement 23 is operated under pressure, the liquid pressure or the gas pressure (depending on which medium is gas or liquid under pressure) does not press against the gap 17 between the anode frame 8 and the anode 7. In this way, the solid electrolyte (e.g., membrane 13) is pressed only against the anode 7 and is mechanically supported on the anode 7. This prevents the solid electrolyte (e.g., membrane 13) from being squeezed or creeping into the gap 17 between the frame 1 (e.g., anode frame 8) and the electrode (e.g., anode 7).
In an alternative embodiment of the frame 1, electrochemical cell 2 and stacked apparatus 23, the anode frame 8 is smaller and the cathode frame 11 is larger. In these alternative embodiments, the step 12 is formed by the anode frame 8. Thus, in the case of a pressure difference, for example a pressure difference of 40 bar, i.e. when only the anode side of the electrochemical cell 2 is operated under pressure, or only the anode side of the stacked arrangement 23 is operated under pressure, the medium pressure does not press against the gap 17 between the cathode frame 11 and the cathode 10. In this way, the solid electrolyte (e.g., membrane 13) is pressed only against the cathode 10 and is mechanically supported on the cathode 10. This prevents the solid electrolyte (e.g., membrane 13) from being pressed or creeping into the gap 17 between the frame 1 (e.g., cathode frame 11) and the electrode (e.g., cathode 11).
In a preferred embodiment, the frame 1 according to the invention comprises two different types of channels for the input and output of water and gas.
The frame 1 preferably comprises one or more I-channels 14 for feeding liquid and gas into the frame 1 and out of the frame 1, respectively. The I-channel 14 is preferably not directly connected to the first opening 6 of the anode frame 8 or the second opening 9 of the cathode frame 11. The core 21 of the anode frame 8 preferably includes one or more I-channels 14. The core 21 of the cathode frame 11 preferably includes one or more I-shaped channels 14. The I-shaped channel 14 is preferably coated with a sealant coating 22.
The frame 1 furthermore preferably comprises one or more type II channels 15 for feeding liquid and gas to the first opening 6, for discharging liquid and gas out of the first opening 6, for feeding liquid and gas to the second opening 9, and for discharging liquid and gas out of the second opening 9. The type II channel 15 preferably connects the type I channel 14 with the first opening 6. Preferably, a type II channel 15 connects the type I channel 14 with the second opening 9.
The liquid and gas input and output will also vary according to the application.
In a preferred embodiment, the sealing material coating 22 applied to all or part of the anode frame 8 includes one or more type II channels 15. In other embodiments, the core 21 of the anode frame 8 includes one or more type II channels 15. In a preferred embodiment, all or part of the coated sealant coating 22 of the cathode frame 11 includes one or more type II channels 15. In other embodiments, the core 21 of the cathode frame 11 includes one or more type II channels 15. The advantage of this embodiment is the low manufacturing cost. In the preferred embodiment, the type II channels 15 are not milled from each anode frame 8 and each cathode frame 11, but are transferred to a tool at once. For example, a negative mold of the anode frame 8 or a negative mold of the cathode frame 11 is a suitable tool. For example, the arrangement, diameter, length and possibly other parameters of the type II channels 15 are transferred to the tool. The tool may be used to transfer the type II channels 15 into the seal 22, for example, as if they were stamped into the sealing material (preferably rubber, such as ethylene propylene diene monomer) with a stamp. The core 21 of the anode frame 8 or the cathode frame 11 is wrapped by vulcanization by means of a tool.
In a preferred embodiment of the frame 1, the anode frame 8 comprises one or more type II channels 15 on the surface of the first side 4 of the frame, which channels are connected to the type I channels 14 and connect the type I channels 14 to the first opening 6, which channels are arranged in the direction of the BPP16 when the frame 1 is mounted in the electrochemical cell 2 or the stacked device 23, wherein the side 4 "of the anode frame opposite to the first side of the frame does not comprise type II channels 15.
In a preferred embodiment of the frame 1, the cathode frame 11 comprises one or more type II channels 15 on the surface of the second side 5 of the frame, which channels are connected to the type I channels 14 and connect the type I channels 14 to the second opening 9, which channels are arranged in the direction of the BPP16 when the frame 1 is mounted in the electrochemical cell 2 or the stacked device 23, wherein the side 5 "of the cathode frame opposite to the second side of the frame does not comprise type II channels 15.
In a preferred embodiment, the frame 1 according to the invention comprises one or more I-channels 14 for the input and output of liquids and gases and one or more II-channels 15 for the input and output of liquids and gases, wherein the one or more I-channels 14 are not connected to the first opening 6 in the anode frame 8 or to the second opening 9 in the cathode frame 11. In a preferred embodiment of the frame 1, the anode frame 8 comprises one or more type II channels 15 on the surface of the first side 4, which channels are connected to one or more type I channels 14 and which connect the one or more type I channels 14 to the first opening 6, which channels are arranged in a direction towards the BPP16 when the frame 1 is mounted in the electrochemical cell2 or the stacked device 23, wherein the side 4 "opposite to the first side 4 of the anode frame does not comprise any type II channels 15. In a preferred embodiment of the frame 1, the cathode frame 11 comprises one or more type II channels 15 on the surface of the second side 5, which channels are connected to one or more type I channels 14 and connect the one or more type I channels 14 to the second opening 9, which channels are arranged towards the BPP16 when the frame 1 is mounted in the electrochemical cell2 or the stacked arrangement 23, wherein the side 5 "opposite to the second side 5 of the cathode frame does not comprise any type II channels 15.
In a preferred embodiment, the frame 1 according to the invention comprises at least two I-channels 14 for the input and output of liquids and gases and at least two II-channels 15 for the input and output of liquids and gases, wherein the I-channels 14 are not connected to the first opening 6 of the anode frame 8 or to the second opening 9 of the cathode frame 11. In a preferred embodiment of the frame 1, the anode frame 8 comprises at least two type II channels 15 on the surface of the first side of the frame 4, which channels are connected to at least two type I channels 14 and connect the type I channels 14 to the first opening 6, which channels are arranged towards the BPP16 when the frame 1 is mounted in the electrochemical cell 2 or the stacked device 23, wherein the side 4 "opposite to the first side of the frame of the anode frame does not comprise type II channels 15. Preferably, a plurality of type II channels 15 are arranged on the first side 4 of the frame, connecting the type I channels 14 with the first opening 6. In a preferred embodiment of the frame 1, the cathode frame 11 comprises at least two type II channels 15 on the surface of the second side 5 of the frame, which channels are connected to at least two type I channels 14 and connect the type I channels 14 to the second opening 9, which channels are arranged towards the BPP16 when the frame 1 is mounted in the electrochemical cell 2 or the stacked device 23, wherein the side 5 "of the cathode frame opposite to the second side of the frame does not comprise type II channels 15. Preferably, a plurality of type II channels 15 are arranged on the second side 5 of the frame, connecting the type I channels 14 with the second opening 9.
The type II channels 15 connect the type I channels 14 with the first opening 6 and the second opening 9, i.e. the type II channels 15 connecting the type I channels 14 with the anode 7 and the cathode 10 are used for inputting and outputting liquid and gas, which type II channels 15 are arranged in the anode frame 8 and/or the cathode frame 11 so as to be directed in the direction of the BPP16 instead of in the direction of the solid electrolyte, e.g. the membrane 13. If a gas or liquid flows through the type I channels 14, the solid electrolyte (e.g. membrane 13) is not affected, since the side of the anode frame 7 and the side of the cathode frame 11 where the solid electrolyte (e.g. membrane 13) is located is free of any type II channels 15, i.e. no type II channels 15 are present in the immediate area of the first opening 6 or the second opening 9, where the solid electrolyte (e.g. membrane 13) is arranged and where it is exposed to a differential pressure of up to 40 bar during electrolysis. The solid electrolyte (e.g. membrane 13) is located on a smooth plane without channels and is therefore well supported even at differential pressures of up to 40 bar. Meanwhile, the anode chamber (anode chamber is constituted by the anode frame 7, solid electrolyte (e.g., membrane 13) and BPP 16), the cathode chamber (cathode chamber is constituted by the cathode frame 11, solid electrolyte (e.g., membrane 13) and BPP 16), and the entire electrochemical cell 2 can be completely sealed even under a pressure difference of up to 40 bar, without leakage of gas or liquid.
In exemplary embodiments, the frame 1 includes two to one thousand or more type II channels 15, such as at least one hundred type II channels 15, preferably at least two hundred type II channels 15, or more or less, such as 50 or less. Preferably at least half of the type I channels 14 are connected to the first opening 6 or the second opening 9 via type II channels 15. Preferably at least two or more, e.g. four, 10 or more, type II channels 15 connect the type I channel 14 with the first opening 6. Preferably at least two or more, for example four, 10 or more, type II channels 15 connect the type I channel 14 to the second opening 9.
For example, a type II channel 15 connected to the first opening 6 is arranged adjacent to the first side 4 of the frame. The distance between two adjacent type II channels 15 is, for example, 5mm or less, 3mm or less, preferably 2mm or less. For example, the type II channel 15 between the type I channel 14 and the first opening 6 is arranged in a fan-shaped manner at the first side 4 of the frame.
For example, a type II channel 15 connected to the second opening 9 is arranged adjacent to the second side 5 of the frame. The distance between two adjacent type II channels 15 is, for example, 5mm or less, 3mm or less, preferably 2mm or less. For example, the type II channel 15 between the type I channel 14 and the second opening 9 is arranged in a fan-shaped manner at the second side 5 of the frame.
The channels of the frame 1 are designed such that liquid is distributed in the stacked arrangement 23 through the type I channels 14 and liquid reaches each individual electrochemical cell 2 through the type II channels 15. The I-channels 14 are preferably arranged at regular intervals along or parallel to the first opening 6 in the anode frame 8. The I-shaped channels 14 are preferably arranged at regular intervals along or parallel to the second opening 9 of the cathode frame 11. For example, there are 20 or more or less, e.g. 5I-channels 14, on each side of the square first opening 6 or on each side of the square second opening 9.
In a particularly preferred embodiment, the arrangement of the I-channels 14 is such that they supply the same part and thus the same area of the inflow medium (liquid, gas) to the first opening 6 and the second opening 9 of the electrochemical cell 2 or the first opening 6 and the second opening 9 of the stacked device 23, respectively.
In a particularly preferred embodiment, the opening diameter is preferably constant at 5mm or less, in particular less than 2mm, a continuous type II channel 15 leading from each type I channel 14 or a part of the type I channel 14 to the first opening 6 or the second opening 9. For example, these type II channels 15 are arranged in a fan shape such that the type II channels 15 are evenly distributed over the first opening 6 or the second opening 9. Other arrangements of the type II channel 15 are also possible in the area between the first opening 6 or the second opening and the type I channel 14 through the type II channel 15. By limiting the width of the type II channel 15 to 5mm or less, preferably 2mm or less, a sufficient contact pressure can be transmitted to the opposite frame 1 in the region of the type II channel 15.
The type I channels 14 and the type II channels 15 are distributed uniformly over the entire width of the frame 1 along the first opening 6 or the second opening 9, for example over the entire width of the first side 27 of the first opening and over the entire width of the third side 29 of the first opening (fig. 10 a), so that the distribution of the liquid over the entire active cell area (=first opening 6+second opening 9) of the electrochemical cell 2 is particularly uniform. The liquid flows uniformly through the electrochemical cell 2. Since most of the inflowing liquid is used for cooling, uniform distribution of the type II channels 15 can achieve uniform heat dissipation. This arrangement of the type II channels 15 allows for uniform dissipation of heat generated during the electrochemical reaction. The dissipation of the heat of reaction is a critical parameter for the electrochemical cell 2 or the stacked device 23.
According to the invention, the stacked apparatus 23 has different designs and structures.
Including the frame 1, electrochemical cells 2, preassembled modules 20, and stacked devices 23, each type II channel 15 may provide a higher or lower fluid flow pressure drop than each frame 1, each electrochemical cell 2, and other type II channels 15 of each stacked device 23. For example, the external type II channel 15 may be adapted accordingly, e.g. the type II channel 15 at the arrangement edge of the type II channel 15 at the first side 4 of the frame, e.g. the type II channel 15 at the arrangement edge of the type II channel 15 at the second side 4 of the frame, e.g. the type II channel 15 at the arrangement edge of the first side with respect to the first opening 27 is adapted to produce a higher or lower pressure loss of the flowing liquid than the other type II channels 15 of the frame 1, the electrochemical cell 2, the pre-assembly module 20, the stacked arrangement 23. This can be achieved, for example, by reducing the open cross section of the type II channel 15. For example, if the pressure loss in the type I channel 14 is uneven and the type II channel 15 is even, the water volume flow rate of some active cell areas (active cell area=first opening 6+second opening 9) will be higher in the type II channel 15 connected to the type I channel 14 through which the water flows at a higher pressure. If the type II channels 15 are not tuned, the cooling of the active cell area may become more non-uniform, for example, due to the flow of liquid therethrough. This can be compensated for by adjusting the type II channel 15. For example, the cross-section of the associated type II channel 15 may be adjusted, e.g., reduced, to compensate for differences in fluid pressure in the type I channel 14. Preferably, a uniform or consistent fluid pressure is generated throughout the active cell area. By individually adjusting the type II channels 15, for example, the type II channels 15 having different opening cross sections, it is possible to compensate for different pressure losses in the type I channels 14 and to make the flow through all the type II channels 15 uniform.
According to the invention, comprising a frame 1, electrochemical cells 2, preassembled modules 20 and stacked devices 23, wherein the respective frame 1, the respective electrochemical cell 2, the respective preassembled module 20, the respective stacked device 23 are arranged in such a way that each II channel 15 supplies liquid to an area of the same size as the active cell area.
According to the invention, comprising a frame 1, electrochemical cells 2, preassembled modules 20 and stacked devices 23, wherein the respective frame 1, the respective electrochemical cells 2, the respective preassembled modules 20, the respective II-channels 15 of the respective stacked devices 23 are designed such that all II-channels 15 can deliver the same amount of liquid or gas at the same time, i.e. all II-channels 15 are identical. For example, all of the type II channels 15 have the same cross section in which liquid or gas can flow. The type II channels 15 are preferably arranged such that each type II channel 15 provides the same size of liquid or gas to the active cell area. It is particularly preferred that the type II channels 15 are arranged such that each type II channel 15 provides the same area of liquid or gas to the active cell area and all type II channels 15 are identical. In this way, the entire active cell area can be uniformly supplied with liquid or gas.
The number, shape and arrangement of the type I channels 14 and other parameters related to the type I channels 14 and the number, shape and arrangement of the type II channels 15 and other parameters related to the type II channels 15 may be adjusted as desired, for example, depending on the shape of the frame used.
In the frame 1 of the present invention, the anode frame 8 and the cathode frame 11 are connected to each other by a connecting member. Corresponding connecting elements are known to the person skilled in the art. In a preferred embodiment of the frame 1, the anode frame 8 comprises one or more connecting elements, such as pins 19, and the cathode frame 11 comprises one or more connecting elements, such as holes 18, wherein the pins 19 and the holes 18 are arranged in such a way that the holes 18 in the cathode frame 11 can be inserted onto the pins 19 in the anode frame 8, thereby connecting the anode frame 8 and the cathode frame 11 to each other.
The subject of the invention is an electrochemical cell 2 for operation at a pressure difference of up to 40 bar for generating high pressure gas and liquid, which electrochemical cell 2 comprises a solid electrolyte (e.g. membrane 13), an anode 7, a cathode 10, wherein the electrochemical cell 2 comprises a frame 1 according to the invention, wherein a first opening 6 in an anode frame 8 comprises the anode 7, and a second opening 9 in a cathode frame 11 comprises the cathode 10, wherein the solid electrolyte (e.g. membrane 13) is arranged between a side 4 "opposite to a first side 4 of the frame of the anode frame and a side 5" opposite to a second side 5 of the frame of the cathode frame, wherein one side of the solid electrolyte (e.g. membrane 13) rests on the anode 7 and the other side of the solid electrolyte (e.g. membrane 13) rests on a step 12 and the cathode 10 (fig. 7b and 7 c). When the electrolysis unit 2 is operated under a pressure difference, the pressure difference does not act on the solid electrolyte area, such as the membrane 13, on the gap 17 between the anode frame 8 and the anode 7. This prevents the solid electrolyte (e.g. membrane 13) from being pressed or creeping into the 24 gap 7 (fig. 8 and 8 a).
In a preferred embodiment, the electrochemical cell 2 according to the invention comprises a solid electrolyte, for example a membrane 13 having a thickness of less than 80 μm, for example a membrane 13 having a thickness of 50 μm or less, particularly preferably a membrane 13 having a thickness of less than 20 μm, for example a membrane 13 having a thickness of 15 μm or less. In a particularly preferred embodiment, the electrochemical cell 2 according to the invention comprises a solid electrolyte, such as a membrane 13, preferably an ion-conducting membrane 13 having a thickness of less than 80 μm, such as an ion-conducting membrane 13 having a thickness of 50 μm or less, particularly preferably an ion-conducting membrane 13 having a thickness of less than 20 μm, such as a thickness of 15 μm or less.
In the electrochemical cell 2 according to the invention, the sealing material coating 22 (e.g. the rubber coating of the core 21 of the anode frame 8, preferably the EPDM coating), the sealing material coating 22 (e.g. the rubber coating of the core 21 of the cathode frame 11, preferably the EPDM coating) and the step 12 interact with the solid electrolyte (e.g. the membrane 13) (fig. 7c and 8 a) and completely seal the electrochemical cell 2 and the anode and cathode compartments without pressing or creeping the solid electrolyte (e.g. the membrane 13) into the gap 17 between the anode frame 8 and the anode 7. The special arrangement of the type II channels 15 fully ensures the supply and discharge of liquid and gas, as well as the stability of the solid electrolyte (e.g. membrane 13) and the complete sealing of the electrochemical cell 2. Thus, the frame 1 according to the present invention may use a solid electrolyte, such as a membrane 13 having a thickness of less than 80 μm, such as a thickness of 50 μm or less, preferably a thickness of less than 20 μm, such as a thickness of 15 μm or less. These solid electrolytes, such as membrane 13, are referred to as thin solid electrolytes or membranes 13. With the frame 1 of the present invention, the solid electrolyte (e.g., membrane 13) of the electrochemical cell 2 may be thinner than those commonly used in the art. Furthermore, these electrochemical cells 2 operate in such a way that liquid or gas on one side of the cell accumulates at pressures up to 40 bar without damaging the solid electrolyte, e.g. the membrane 13, and without causing leakage of the electrochemical cell 2.
In a preferred embodiment, the anode 7 is designed such that the BPP16 is connected to the anode 7, which is called BPP/anode 36 according to the invention. The use of the BPP/anode 36 not only facilitates assembly, but also reduces contact resistance between the various components.
In a preferred embodiment, the anode 7 comprises at least one coarse distributor and at least one fine distributor for the treatment of a medium, in particular a liquid. The coarse distributor effectively distributes the liquid over the whole cell area (i.e. the first and second openings 6+ 9). The sub-dispenser delivers liquid to the solid electrolyte, e.g., to the membrane 13, providing good electrical contact to the solid electrolyte, e.g., the membrane 13, while providing mechanical support to the solid electrolyte, e.g., the membrane 13. For example, expanded metal may be used as a coarse distributor of the anode 7. For example, a plate made of sintered powder may be used as a fine distributor of the anode 7. The coarse and fine dispensers, such as expanded metal and sintered metal, may be joined together by resistance welding or the like to produce the anode 7. Alternatively, the powder may be sintered directly onto the expanded metal to produce anode 7. The anode 7 may be connected to the BPP 16. The BPP16 is preferably made of the same material as the anode 7. In a particularly preferred embodiment, the BPP16 and anode 7 are made of titanium. In other preferred embodiments, the BPP16 and anode 7 are made of at least 80% identical material, such as titanium. The connection between the BPP16 and the anode 7 may be achieved by means of resistance welding or the like, preferably welding at several points. In the BPP/anode 36, the surface of the BPP16 corresponds to the outer surface of the frame 1, or the surface of the BPP/anode 36 substantially corresponds to the outer surface of the frame 1. The surface of the anode 7 in the BPP/anode 36 is adapted to fill the first opening 6 or to fit the first opening 6. Only one part of the BPP/anode 36 is required for assembly, and no two parts (BPP 16 and anode 7) are required. This means that one component is saved.
The I-channels 14 along one or both sides of the first opening 6 of the anode frame 8 may also be significantly smaller than the I-channels 14 along the other sides of the first opening of the anode frame 8, depending on whether liquid or gas is being delivered through the electrodes (see fig. 10 b). For example, the I-channel 14 on the cathode side may be significantly smaller than the I-channel 14 on the anode side (see fig. 10 b-10 d). In order to save space and ensure mechanical stability of the frame 1, the I-shaped channel 14 may be designed as a unit instead of a round hole. The I-channel 14 may have different shapes and corresponding adaptations.
The subject of the invention is a preassembled module 20 for manufacturing a stacked device 23, which device 23 comprises a frame 1 according to the invention. For example, the subject of the invention is a preassembled module 20 for manufacturing a stacked device 23, comprising an anode frame 8, a cathode frame 11, a BPP16, an anode 7 and a cathode 10,
Wherein the anode frame 8 comprises a first side 4 of the frame having a planar first surface, a side 4 "opposite the first side 4 of the anode frame, and a first opening 6 for receiving the anode 7, wherein the first opening 6 extends from the first side 4 of the frame to the side 4" opposite the first side 4 of the anode frame, and wherein the first opening 6 is surrounded by the anode frame 8, wherein the anode frame 8 comprises at least one connecting element, such as a pin 19,
Wherein the cathode frame 11 comprises a second side 5 of the frame having a planar second surface, a side 5 "opposite the second side 5 of the frame of the cathode frame, and a second opening 9 for receiving the cathode 10, wherein the second opening 9 extends from the second side 5 of the frame to the side 5" opposite the second side 5 of the frame of the cathode frame, and is surrounded by the cathode frame 11, the cathode frame 11 comprising at least one connecting element for connecting the anode frame 8, for example a hole 18 for receiving a pin 19 of the anode frame 8,
Wherein the BPP16 is arranged between the first side 4 of the frame and the second side 5 of the frame, the BPP16 may be part of a BPP/anode 36,
Wherein the anode frame 8 comprises a core 21 and a sealing material coating 22, wherein the core 21 is fully or partly coated with the sealing material coating 22, wherein, for example, the core 21 comprises or consists of a metal, and the sealing material coating 22 comprises or consists of a sealing material, such as rubber, preferably EPDM, wherein, preferably, the BPP16 is connected with the anode 7 forming a BPP/anode 36, the anode 7 or the BPP/anode 36 is inserted or pressed into the first opening 6, and the anode 7 is framed by the anode frame 8,
The cathode frame 10 comprises a core 21 and a sealing material coating 22, wherein the core 21 is wholly or partly coated with the sealing material coating 22, e.g. the core 21 comprises or consists of a metal, the sealing material coating 22 comprises or consists of a sealing material, e.g. a rubber, preferably EPDM, the cathode 10 being inserted or pressed into the second opening 9 and framed by the cathode frame 11,
Wherein the anode frame 8 and the cathode frame 11 are connected by means of a connecting element of the anode frame 8 and the cathode frame 11, e.g. pins 19 of the anode frame 8 are inserted into holes 18 of the cathode frame 11, whereby the anode frame 8 and the cathode frame 11 are connected to each other,
Wherein the first opening 6 is larger than the second opening 9, the anode frame 8 and the cathode frame 11 are arranged such that the first side 4 of the frame and the second side 5 of the frame form a step 12 at the transition from the anode frame 8 to the cathode frame 11, wherein preferably the step 12 is part of the cathode frame 11, which is preferably adjacent to the second opening 9, and preferably frames the second opening 9, wherein the step 12 preferably forms a planar third surface which acts as a support surface for the solid electrolyte (e.g. membrane 13), wherein the BPP16 of the BPP/anode 36 rests on the anode 7 and the anode frame 8 on one side and on the cathode 10, the cathode frame 11 and the step 12 on the other side. The preassembled module 20 preferably comprises a type I channel 14 and a type II channel 15 as described in the present application for supplying and removing liquid and gas, which may be arranged in the described manner.
The subject of the invention is a method for manufacturing a preassembled module 20 comprising a frame 1 according to the invention. For example, the subject of the invention is a method of manufacturing a preassembled module 20, comprising the following method steps:
a) For the anode frame 8 a core 21 is made, the core 21 preferably being made of metal, the core 21 comprising a first side 4 of the frame having a planar first surface and a side 4 "opposite to the first side 4 of the frame of the anode frame, the first side 4 of the frame and the side 4" opposite to the first side 4 of the frame of the anode frame comprising a first opening 6, the first opening 6 extending from the first side 4 of the frame to the side 4 "opposite to the first side 4 of the frame of the anode frame and being framed by the anode frame 8 and comprising one, two or more I-channels 14 for supplying and removing water and gas, wherein the one or more I-channels 14 are not connected to the first opening 6 in the anode frame 8 and the anode frame 8 comprises at least one connecting element for connection to the cathode frame 11, such as: the pin 19 is provided with a pin opening,
B) The surface of the core 21 produced according to a) for the anode frame 8 is wholly or partly, for example according to a) at least 90% of the surface of the core 21 produced for the anode frame 8, which is used for producing a rubber-made coating as sealing material coating 22 produced by vulcanization, coated with natural or synthetic rubber and then vulcanized, whereby a rubber-made coating, preferably an EPDM-made coating, is produced on the entire surface or part of the surface of the core 21, wherein in the rubber-made coating one or more type II channels 15 are formed on the surface of the first side 4 of the frame, which type II channels 15 are connected to one or more type I channels 14 and which type I channels 14 are connected to the first opening 6, which channels are arranged towards the BPP16 or BPP side of the BPP/anode 36, whereas in the opposite side 4 "of the anode frame from the first side 4,
C) Anode 7 and BPP16 or BPP/anode 36 are placed or pressed into anode frame 8 manufactured according to a) and b),
D) For the cathode frame 11a core 21 is made, the core 21 preferably being made of metal, the core 21 comprising a second side 5 of the frame with a planar second surface and a side 5 "opposite to the second side 5 of the frame of the cathode frame, the second side 5 of the frame and the side 5" opposite to the second side 5 of the frame of the cathode frame comprising a second opening 9, the second opening 9 extending from the second side 5 of the frame to the opposite side 5 "of the second side 5 of the frame of the cathode frame and being framed by the cathode frame 11 and comprising one or more I-channels 14 for supplying and removing water and gas, wherein these I-channels 14 are not connected to the second opening 9 in the cathode frame 11 and the cathode frame 11 comprises at least one connecting element for connecting to the anode frame 8, for example: the openings 18 are provided in the form of holes,
E) At least 90% of the surface of the core 21 produced according to d) for the cathode frame 11, for example according to d), of the core 21 produced for the cathode frame 8, which is used for producing a rubber-made coating as sealing material coating 22 produced by vulcanization, is coated with natural or synthetic rubber and then vulcanized, whereby a rubber-made coating, preferably an EPDM-made coating, is produced on the entire surface or part of the surface of the core 21, wherein in the rubber-made coating one or more type II channels 15 are formed on the surface of the second side 5, which type II channels 15 are connected to one or more type I channels 14 and which type I channels 14 are connected to the second opening 9, in such a way that when the cathode frame 11 is installed in the electrochemical cell 2 or the stacked arrangement 23, the BPP side of BPP16 or BPP/anode 36 is arranged, wherein no type II channels 15 are formed in the side 5 "opposite to the second side 5 of the cathode frame,
F) The cathode frame 11 produced according to d) and e) is connected to the anode frame 8, e.g. the cathode frame 11 is inserted onto the anode frame 8, the BPP16 or the BPP of the BPP/anode 36 is arranged between the first side 4 of the frame and the second side 5 of the frame, and then the cathode 10 is inserted or pressed into the cathode frame 11.
The subject of the invention is a method for manufacturing a stacked device 23 for converting or generating gases and liquids under pressure, comprising a frame 1 according to the invention, a preassembled module 20 according to the invention, an electrochemical cell 2. The subject of the invention is, for example, a method for producing a stacked device 23 for converting or generating high-pressure liquid or high-pressure gas under pressure difference, comprising the following method steps:
a) At least x preassembled modules 20 and at least x+1 solid electrolytes (e.g. at least x+1 membranes 13) according to the invention are stacked alternately up and down, wherein a stack 3 of preassembled modules is produced, in which stack 3 of preassembled modules one preassembled module 20 and one solid electrolyte (e.g. membrane 13) are stacked alternately up and down, one solid electrolyte (e.g. membrane 13) is arranged at the top and bottom of the stack 3 of preassembled modules, respectively, one solid electrolyte (e.g. membrane 13) is arranged between every two adjacent preassembled modules 20, and
B) Then, on one side of the stack 3 of pre-assembled modules, the single anode 7 is arranged parallel to the external solid electrolyte (e.g. membrane 13), on the other side of the stack 3 of pre-assembled modules, the single cathode 10 is arranged parallel to the external solid electrolyte (e.g. membrane 13),
C) The end plates 33 are parallel to the single anode 7, and to the single cathode 10, and the resulting stack is then compressed between the two end plates 33, to form the stacked arrangement 23,
Wherein x is an integer and is not less than 2.
In a preferred embodiment of the method of manufacturing a stacked device 23 according to the present invention, one or more, preferably each x+1 solid state electrolyte, e.g. each x+1 film 13, in the stacked device 23 has a thickness of less than 80 μm, preferably a thickness of less than 50 μm or less, more preferably a thickness of less than 20 μm or less, e.g. 15 μm or less, wherein x is an integer and ≡2.
The subject of the invention is a stacked device 23 for converting or generating high-pressure liquid or high-pressure gas operating under pressure differential, which device comprises one or more frames 1 according to the invention. The subject of the invention is a stacked device 23 comprising one or more pre-assembled modules 20 according to the invention. The subject of the invention is a stacked device 23 comprising one or more electrochemical cells 2 according to the invention.
For example, the subject of the invention is a stacked device 23 for converting or generating high-pressure liquid or high-pressure gas under pressure difference, comprising x preassembled modules 20 according to the invention, x+1 solid electrolytes (for example each of the x+1 membranes 13), one anode 7', one cathode 10' and two end plates 33, wherein x preassembled modules 20 and x+1 solid electrolytes (for example the x+1 membranes 13) are stacked alternately one after the other to form a stack 3 of preassembled modules, in which stack 3 of preassembled modules there is in each case one preassembled module 20 and x+1 membrane 13 stacked alternately one above the other to form a stack 3 of preassembled modules, wherein one preassembled module 20 and one solid electrolyte (for example membrane 13) are stacked alternately one above the other, forming a stack 3 of pre-assembled modules, wherein one solid electrolyte (e.g. membrane 13) is alternately stacked in the stack of pre-assembled modules 3, one solid electrolyte (e.g. membrane 13) is arranged at the top and bottom of the stack 3 of pre-assembled modules, respectively, one solid electrolyte (e.g. membrane 13) is arranged between each two adjacent pre-assembled modules 20, wherein a single anode 7' is arranged parallel to the outer solid electrolyte (e.g. membrane 13) on one side of the stack 3 of pre-assembled modules, a single cathode 10' is arranged parallel to the outer CCM13 on the other side of the stack 3 of pre-assembled modules, wherein one end plate 33 is arranged parallel to the single cathode 10', the resulting stack is compressed between the two end plates 33 to form a stacked arrangement 23,
Wherein x is an integer and is not less than 2.
In a preferred embodiment of the stacked device 23 according to the invention, one or more of the stacked devices 23, preferably each of the x+1 solid electrolytes, e.g. each of the x+1 membranes 13, has a thickness of less than 80 μm, preferably a thickness of less than 50 μm or less, particularly preferably a thickness of less than 20 μm or less, e.g. a thickness of 15 μm or less, wherein x is an integer and ≡2.
Other components may also be mounted in place of the stacked apparatus 23 as desired, for example, an insulating plate 32 may be mounted between the solid electrolyte (e.g., membrane 13) and the end plate 33. Insulation plates 32 in these positions prevent shorting of end plates 33, for example when screws are used. Corresponding components are known to the person skilled in the art. The skilled person can adapt the manufacturing method accordingly.
Another subject of the invention is a stacked arrangement 23 for converting or generating high-pressure liquid or gas under pressure difference, comprising x pre-assembled modules 20, x+1 solid electrolytes (e.g. membranes 13), one anode 7, one cathode 10' and two end plates 33 according to the invention, wherein x pre-assembled modules 20 and x+1 solid electrolytes (e.g. membranes 13) are stacked alternately to form a stack 3 of pre-assembled modules, in which stack 3 of pre-assembled modules one pre-assembled module 20 and one solid electrolyte (e.g. membrane 13) are stacked together in each case, wherein one solid electrolyte (e.g. membrane 13) is arranged at the top and bottom of the stack 3 of pre-assembled modules, respectively, and in each case one solid electrolyte (e.g. membrane 13) is arranged between each two adjacent pre-assembled modules 20, wherein on one side of the pre-assembled modules ' stacks 3 half-cell anodes are arranged parallel to the external solid electrolytes (e.g. membrane 13) and on the other side of the pre-assembled modules ' stacks 3 half-cell cathodes are arranged parallel to the external solid electrolytes (e.g. membrane 13),
Wherein the end plates 33 are parallel to the half-cell anodes and parallel to the half-cell cathodes, the resulting stack is compressed between the two end plates 33, to form the stacked arrangement 23,
Wherein x is an integer not less than 2.
The half cell anode comprises only the anode side of the electrochemical cell 2 and does not comprise the cathode side of the electrochemical cell 2. In a preferred embodiment, the half-cell anode comprises a single anode 7' and an anode frame 8. In a preferred embodiment, the half-cell anode consists of a single anode 7' and an anode frame 8. The half-cell anode completes one electrochemical cell 2 in one preassembled module 20 or stack 3 of preassembled modules.
The half cell cathode comprises only the cathode side of the electrochemical cell 2 and does not comprise the anode side of the electrochemical cell 2. In the preferred embodiment, the half cell cathode comprises a cathode 10' and a cathode frame 11. In a preferred embodiment, the half cell cathode consists of a single cathode 10' and a cathode frame 8. The half cell cathode completes the electrochemical cell 2 in the preassembled module 20 or stack 3 of preassembled modules.
In a preferred embodiment, the stacked apparatus 23 comprises at least 2 or 3 or 5 or more, for example 10, 50, 100, 500, 1000 or more modules 20 pre-assembled according to the invention. Preferably, the stacked apparatus 23 according to the present invention comprises, in addition to x pre-assembled modules 20 according to the present invention (where x is an integer and ≡2), a cathode frame 11, a solid electrolyte (e.g. membrane 13), an anode frame 8 and two end plates 33. In the stacked device 23, the first and last electrochemical units 2 are preferably different from the middle electrochemical unit according to the invention. For example, to produce the stacked apparatus 23, it is necessary to arrange a solid electrolyte (e.g., the membrane 13) on the cathode frame 11, alternately stack x pre-assembled modules 20 and x solid electrolytes (e.g., the membrane 13) on the solid electrolyte (e.g., the membrane 13), and stack the anode frame 8 thereon. The stack is compressed between end plates 33 to form stacked apparatus 23, where x is an integer and ≡2.
In the stacked arrangement 23, one of the two end plates 33 is preferably an upper end plate 38, for example, in the stacked arrangement 23 the upper end plate 38 is arranged on top. In the stacked apparatus 23, one of the two end plates 33 is preferably a lower end plate 44, for example in the stacked apparatus 23, the lower end plate 44 is located at the bottom.
The stacked apparatus 23 preferably operates as a flow reactor. Liquid and/or gas is continuously fed into the stacked apparatus 23 and liquid and/or gas is continuously discharged from the stacked apparatus 23. Liquid must be dispensed from the liquid inlet 39 (=liquid inlet interface) of the stacked apparatus 23 to the I-channel 14. At the same time, liquid must be transported from the I-channel 14 to a drain 40 (=liquid connection outlet) for draining the liquid. This requires space on the end plate 33, but there may be no such space on the end plate 33, e.g. the end plate 33 may become too thick and if the end plate 33 is too thick the stacked arrangement 23 may become too heavy.
The subject of the invention is a cover 37 for a stacked device 23 device. According to the present invention, the cover 37 is constructed to create as much space as possible for the liquid without making the entire end plate 33 unnecessarily thick.
The subject of the invention is a cover 37 for a stacked apparatus 23, wherein an end plate 33, for example an upper end plate 38, comprises at least one water connection 39 for introducing liquid, at least one drain 40 for draining liquid and at least two distribution covers 41, wherein the upper end plate 38 for creating a liquid space has at least two spaces for distributing liquid in an upper end plate 42, wherein each of the at least two distribution covers 41 has a space for distributing liquid in a distribution cover 43, wherein at least one distribution cover 43 for introducing liquid into the stacked apparatus 23 is connected to at least one water connection 39 for introducing liquid and to a liquid distribution space in the end plate 42, wherein at least one further distribution cover 43 for draining liquid out of the stacked apparatus 23 is connected to at least one drain 40 for draining liquid and to a liquid distribution space in the end plate 42.
The subject of the invention is a stacked device 23 comprising a cover 37 according to the invention. The object of the invention is a stacked device 23 according to the invention comprising a cover 3 according to the invention.
In order to completely seal the individual frames 1 of the electrochemical cells 2 and the individual frames 1 of the stacked arrangement 23, in particular under high pressure or high pressure differential conditions, the end plates 33 must be tensioned with sufficient bolt force or contact pressure. Then, the coating layer 22 made of a sealing material plays a role of sealing the individual frame 1, the anode frame 8, and the cathode frame 11 completely. If the frame surface of the frame 1 is large, the contact pressure required to clamp the end plate 33 to completely seal it will be greater. For frames 1 with a larger frame area, the contact pressure is particularly high if the core 21 of the anode frame and the core 21 of the cathode frame are completely coated with a coating 22 of sealing material, i.e. the first side of the frame 4 of the anode frame 8 has a larger area of sealing material coating 22, the first opening 6 is larger, i.e. the first side of the first opening 27 is longer, and the second side of the first opening 28 may also be longer. For example, a large frame area refers to 1600cm 2 or more. In a preferred embodiment, not the entire frame surface of the anode frame 8 needs to be sealed. In some embodiments, not the entire frame surface of cathode frame 11 is required for sealing. In order to reduce the contact pressure, the thickness of the sealing material coating 22 may be reduced in the surface area of the core 21 where sealing is not required. The respective anode frame 8 or cathode frame 11 comprises areas of the core 21 in which the sealing material coating 22 has a certain layer thickness and areas comprising a coating 22' of sealing material in which the sealing material coating 22 "has a reduced layer thickness compared to the layer thickness of the sealing material coating 22 (fig. 10b, fig. 14), for example in areas of the core 21 surface where sealing is not required, the sealing material coating 22" has a layer thickness of 0.05mm or more, for example 0.1mm, preferably 0.2mm or more, which is smaller than the layer thickness of the sealing material coating 22 in areas of the core 21 surface where sealing of the active areas (active area = first and second openings 6+ 9) and type I and type II channels 14+15 is required. In order to reduce the contact pressure, the thickness of the coating layer 22 made of the sealing material may be reduced on the surface of the core 21 of the cathode frame 11 or the anode frame 8, which is not necessary for sealing, for example, in the surface area of the core 21 where sealing is not necessary, the thickness of the coating layer 22″ of the sealing material is reduced by 0.05mm or more, for example, 0.1mm, preferably 0.2mm or more, for example, in the surface area of the core 21 where sealing is not necessary (the first and second openings 6+9) and the type I and type II channels 14+15.
The areas of the surface of the core 21 of the anode frame 8 and/or the cathode frame 11 not reduced in thickness by the sealing material coating 22 are mainly subjected to pressure (fig. 1, 10 to 15 MPa) when clamping the stacked apparatus 23. For example, a sealing area of the surface of the core 21 having an unrefined layer thickness by the sealing material coating 22 may be defined as, for example, an area of the surface of the core 21 surrounding the first inner opening 6 or the second inner opening 9 and the distance of the type I channel 14 and the type II channel 15 of 0.2mm or more, such as 0.5mm or 1mm or more, preferably 1.5mm or 2mm or more (fig. 10b, fig. 14). The distance may be different. The distance may be the same or different to the first opening 6, the second opening 9, the arrangement of the type I channels 14, the areas of the type II channels 15 in which the layer thickness is not reduced by the sealing material coating 22. In a particular embodiment, the sealing material coating 22 may have a reduced layer thickness of the sealing material coating 22 "in the surface area or part of the surface area of the core 21 of the anode frame 8 or cathode frame 11, i.e. in this surface area the core 21 is not coated with the coating 22 of sealing material, the layer thickness of which is zero. By reducing the layer thickness of the sealing material coating layer 22 in some areas of the surface of the core 21 of the anode frame 8 or the cathode frame 11, the area required for compaction can be reduced by 50% compared to the sealing material coating layer 22 that completely covers the surface of the core 21 with the same layer thickness. In this way, the contact pressure required for pressing the frame 1 in the stacked apparatus 23 can also be reduced by 50%.
Preferably, the stacked device 23 according to the invention is used for the electrolysis of liquids in a temperature range of 10 to 95 degrees celsius, preferably in a temperature range of 40 to 80 degrees celsius, particularly preferably in a temperature range of 68 to 72 degrees celsius. The stacked device 23 according to the invention has the further advantage that the temperature difference from one side of the stack to the other side of the stack is preferably at most 0 to 10 degrees celsius, preferably at most 3 to 7 degrees celsius, particularly preferably at most 4 degrees celsius.
Another advantage of an advantageous embodiment of the present invention is the low manufacturing cost. In the preferred embodiment, the type II channels 15 are not milled from each anode frame 8 and each cathode frame 11, but are transferred to a tool at once. One suitable tool is the negative mould of the anode frame 8 and the other tool is the negative mould of the cathode frame 11. For example, the arrangement, diameter, length and possibly other parameters of the type II channels 15 are transferred to the tool. With this tool the type II channels 15 can be transferred into the sealing member 22, for example as if they were stamped into the sealing material with a stamp, preferably rubber, for example EPDM. By means of a tool, the core 21 of the anode frame 8 or the core 21 of the cathode frame 11 is coated with a seal 22 by means of vulcanization, while the desired structure is formed on the seal 22, for example forming the type II channels 15 on the first side 4 of the frame or the second side 5 of the frame. In the manufacturing method of such a frame 1, it is preferable to use a seal member 22 made of rubber (for example EPDM). In this embodiment, the core 21 is coated with the sealing member 22, so that the type II channel 15 can be simultaneously produced in a desired area of the anode frame 8 and/or the cathode frame 11 according to the present invention. The molded article or rubber molded article produced by vulcanization of the anode frame 8 and/or the cathode frame 11 can be used as it is and can be mass-produced at low cost. Other processes are also known, such as injection molding or 3D printing.
Preferably, the stacked apparatus 23 is designed such that all components have smooth and uniform surfaces so that no voltage peaks occur on the solid electrolyte (e.g., membrane 13). To prevent the solid electrolyte (e.g. membrane 13) from being pressed or creeping into 24 the pores of anode 7 and/or cathode 10 under moderate pressure, for example, anodes 7 and/or cathodes 10 with pore diameters less than 0.1mm are used.
Since the sealing member 22 and the anode frame 8 or the sealing member 22 and the cathode frame 11 are each composed of one piece, the anode frame 8 and the cathode frame 11 can be easily connected together to form one pre-assembled module 20. To produce the preassembled module 20, a BPP16, i.e. BPP/anode 36, is preferably used in connection with the anode 7. For example, the BPP16 and anode 7 are welded together such that the BPP16 and anode 7 are formed as a single component BPP/anode 36. To produce the preassembled module 20, the anode frame 8 is first inserted or pressed onto the anode 7 or the anode 7 of the BPP/anode 36. For example, the anode frame 8 may have, in addition to the first pin 19 as a connection with the cathode frame 11, a second pin 19 as a connection with the BPP16 or the BPP/anode 36, which pin may be inserted into the BPP 16. To this end, the BPP16 or the BPP/anode 36 BPP16 comprises a corresponding means for connection with the anode frame 8, preferably a hole 18. The anode frame 8 with the inserted or pressed anode 7 and BPP16 or BPP/anode 36 is then turned over and the cathode frame 11 is also inserted on the other side of the anode frame 8 with means, preferably holes 18, connected to the anode frame 8. The cathode 10 is then inserted or pressed into the cathode frame 11 (fig. 6). This results in a preassembled module 20. The pre-assembled modules 20 may then be stacked alternately with a solid electrolyte (e.g. membrane 13), for example by centring pins, in order to manufacture the stacks 3 of pre-assembled modules or the stacked arrangement 23.
List of reference numerals
Description of the drawings:
Fig. 1: the classical structure of the electrochemical cell of the prior art comprises a frame 1, a solid electrolyte (e.g. membrane 13), a bipolar plate (BPP) 16, an anode 7, a cathode 10, and a gap 17 between the frame 1 and the anode 7 and a gap 17 between the frame 1 and the cathode 10. The frame 1 shown in the figures comprises an I-channel 14 for the input and output of water and gas.
Fig. 2: according to the frame 1 in fig. 1, a deformation of the frame 1 is shown, forming a larger gap 17 between the frame 1 and the anode 7 and between the frame 1 and the cathode 10, and a creeping 24 of solid electrolyte (e.g. membrane 13) enters the frame 1 and the anode 7 and an enlarged gap 17 between the frame 1 and the cathode 10.
Fig. 3a: a portion of a frame 1 made in accordance with the present invention is shown comprising a core 21 coated with a coating of sealing material 22, including a type II channel 15 in the sealing material coating 22.
Fig. 3b: a part of the frame 1 of the invention is shown. The frame 1 comprises a core 21 coated with a sealing material coating 22 and a part of the type II channel 15 in the sealing material coating 22.
Fig. 4: the cathode frame 11 according to the invention has a second opening 9, which is surrounded by a first side 27', a second side 28', a third side 29 'and a fourth side 30' of the cathode frame 11. The cathode frame 11 comprises two holes 18 as connection elements to the anode frame 8 and 20I-channels 14. The second side 5 of the cathode frame 11 comprises a plurality of type II channels 15 connecting the second opening 9 with ten type I channels 14, each type I channel 14 being connected to the second opening 9 by a plurality of type II channels 15. On the side 5 "opposite to the second side 5 of the cathode frame there is no type II channel 15 connecting the type I channel 14 and the second opening 9.
Fig. 5: the anode frame 8 according to the invention has a first opening 6, which is surrounded by a first side 27, a second side 28, a third side 29 and a fourth side 30 of the anode frame 8. The anode frame 8 comprises two pins 19 as connecting elements with the cathode frame 11, in this particular example 20I-channels 14, which are arranged in such a way that they can interact with the 20I-channels 14 of the cathode frame 11 when the anode frame 8 and the cathode frame 11 are connected, to supply and remove liquid and gas. The first side 4 of the anode frame 8 comprises a type II channel 15 connecting the first opening 6 with ten type I channels 14. On the side 4 "opposite to the first side 4 of the anode frame there is no type II channel 15 connecting the type I channel 14 with the first opening 6. The anode frame 8 comprises a coating 22 made of a sealing material, preferably rubber. The anode frame 8 comprises a lip made of sealing material, preferably a rubber lip 25.
Fig. 6: a method of manufacturing a pre-assembled module 20 is schematically shown, with the following process steps: a) Initial position: anode 7 and BPP16 connections (BPP/anode 36); b) The first step: the pin 19 of the anode frame 8 is inserted into the hole 18 of the BPP/anode 36; c) And a second step of: flipping the arrangement in b), the BPP16 side of the BPP/anode 36 can be seen; d) And a third step of: inserting the cathode frame 11 into the arrangement; e) Fourth step: the cathode 10 is inserted into the second opening 9.
Fig. 7: a cross-sectional view of the preassembled module 20 is shown. The individual components of the preassembled module 20 can be seen from the figure: cathode frame 11, anode frame 8, BPP/anode 36, cathode 10, and arrangement of cathode frame 11, anode frame 8, BPP/anode 36, and cathode 10 in preassembled module 20. The preferred sequence of assembly of the various components is also shown. The type II channel 15 in the cathode frame 11 is arranged on the opposite side of the visible side of the cathode frame 11. This is the second side 5 of the frame. From this point of view they are not visible. On the side 5″ opposite the second side of the frame of the cathode frame, their arrangement on the second side 5 of the frame is marked in light grey.
Fig. 7a: a plan view of the preassembled module 20 is shown. Four parts belonging to the preassembled module 20 can be seen: cathode frame 11, anode frame 8, BPP/anode 36, and cathode 10. The type II channels 15 are all arranged in the direction of the BPP/anode 36 and are therefore not visible in the pre-assembled assembly 20, as they are arranged inside the pre-assembled assembly 20. The arrangement of the type II channels 15 inside the assembly 20 is shown in light grey on the visible side of the cathode frame 11 (=the side opposite to the second side of the cathode frame=5 ").
Fig. 7b shows a side view of the preassembled module 20. The anode frame 8 and the cathode frame 11 are connected together. The anode 7 is inserted into the anode frame 8 and the cathode 10 is inserted into the cathode frame 11. The BPP16 is located between the anode frame 8 and the cathode frame 11. Since the first opening 6 is larger than the second opening 9, the anode frame 8 and the cathode frame 11 form one step 12. The BPP16 is located on the cathode 10, the step 12 and the cathode frame 11, and the other side is located on the anode 7 and the anode frame 8.
Fig. 7c: an enlarged cross-sectional view of the portion of the preassembled module 20 of fig. 7b is shown, clearly showing the step 12.
Fig. 8: a schematic structural diagram of a stacked device 23, i.e. a stack 3 of pre-assembled modules, designed according to the invention is shown. Shown is a stack with three electrochemical cells 2. Arrows indicate the direction of the gas pressure during high pressure liquid electrolysis, which is carried out at a pressure difference of 40 bar.
Fig. 8a: an enlarged cross-sectional view of a portion of the electrochemical cell 2 with a step 12 is shown. Arrows indicate the direction in which the increased pressure acts on the solid electrolyte (e.g., membrane 13) under the action of the pressure differential.
Fig. 9a: example dimensions of the cathode frame 11. The type II channel 15 connects the second opening 9 with the type I channel 14, the type I channel 14 being arranged along a second side 28 'of the second opening and a fourth side 30' of the second opening. In each case there are a plurality of type II channels 15 connecting the second opening 9 with the type I channels 14. The respective II-type channels 15 are separated by a projection 26.
Fig. 9b: example dimensions of the anode frame 8 match the cathode frame 11 shown in fig. 9 a. The type II channel 15 connects the first opening 6 with the type I channel 14, the type I channel 14 being arranged along a first side 27 of the first opening and a third side 29 of the first opening. In each case there are a plurality of type II channels 15 connecting the first opening 6 with the type I channel 14. The respective II-type channels 15 are separated by a projection 26.
Fig. 10a: an embodiment of an anode frame 8 is shown. The anode frame 8 comprises type I channels 14 and type II channels 15, wherein the type II channels 14 are arranged in a fan-shape on the first side 4 of the frame. In the present embodiment, the anode frame 8 is quadrangular, comprising a quadrangular first opening 6 and twenty I-channels 14, wherein the five I-channels 14 are arranged on four sides of the anode frame, respectively, i.e. the first side 27 of the first opening comprises five I-channels 14, the second side 28 of the first opening comprises five I-channels 14, the third side 29 of the first opening comprises five I-channels 14, and the fourth side 30 of the first opening comprises five I-channels 14. On two opposite sides of the anode frame 8, five type I channels 14 are connected to eight type II channels 15, respectively. Each type II channel 15 is connected to one type I channel 14 and the first opening 6. The type II channels 15 are arranged in a fan-like pattern on the first side 4 of the frame and are evenly distributed along the first side 27 of the first opening and the third side 29 of the first opening.
Fig. 10b: an anode frame 8 is shown. The anode frame 8 includes an I-shaped channel 14, wherein a portion of the I-shaped channel 14 is circular and another portion is elliptical. The anode frame 8 comprises a coating 22 made of a sealing material, which coating is arranged on a core 21 (core not shown) of the anode frame 8. The coating 22 made of sealing material has a defined layer thickness, shown as a border area. The line around the delineated area is an annular protrusion 26 to increase the sealing effect around the active area 26 ". The type I channel 14 and type II channel 15 of the anode frame 8 and the surrounding area of the first opening 6 are coated with a coating 22 made of a sealing material, the thickness of which has been determined. The thickness of the sealing material coating 22 "of the remaining part of the core 21 of the anode frame 6 (indicated as 22' outside the border) is smaller than the thickness of the prescribed sealing material coating 22.
Fig. 10c: an oblique side view of the anode frame 8. The figure shows a type II channel 15 which is designed as a recess in the sealing material coating 22, the sealing material coating 22 having a defined layer thickness in this region of the anode frame 8. Adjacent type II channels 15 are separated by a protrusion (=a region where the coating 22 made of a sealing material has a prescribed thickness).
Fig. 10d shows a cross-section of the anode frame 8 of fig. 10 c.
Fig. 10e: a cathode frame 11 is shown. The cathode frame 11 includes I-shaped channels 14, some of which 14 are circular and others of which 14 are elliptical. An oval I-shaped channel 14 is connected to the second opening 9 via a II-shaped channel 15. The cathode frame 11 includes a rubber lip 25 for isolating the single voltage measurement. The anode frame 8 is similarly arranged.
Fig. 11 shows an embodiment of a preassembled module 20 consisting of a cathode frame 11 and an anode frame 8 (without cathode 10 and without solid electrolyte, e.g. without membrane 13 in the figure). The step 12 is formed by a first opening 6 and a second opening 9 of different sizes. On a part of the step 12, a type II channel 15 is arranged, and only a part of the type II channel 15 is visible due to being blocked by the cathode frame 11.
Fig. 12 shows a stacked device 23 designed according to the present invention, comprising stacked electrochemical cells 2, insulating plates 32, end plates 33, tie rods 34 and collector plates 35.
Fig. 13 shows a preferred embodiment of anode 7 wherein BPP16 is connected to anode 7 to form BPP/anode 36.
Fig. 14 shows the pressure distribution of the electrochemical cell 2 according to the invention in the anode frame 8 as shown in fig. 10 b. In the region of the anode frame 8, i.e. for example along the first side 27 of the first opening and along the second side 29 of the first opening and around the I-channel 14, the core 21 is coated with a coating 22 of sealing material, which has a layer thickness, in which region the pressure is at most 10 to 15MPa. The region in which the type II channel 15 connecting the first opening 6 and the type I channel 14 and the protrusion 26 are located is not included. . The pressure in this zone is only 1 to 2MPa. In the outer edge region of the anode frame 8, the coating thickness of the core 21 is reduced compared to the sealing material coating 22 (=reduced layer thickness of the sealing material coating 22 "), the pressure of which region is lower, 0.1 to 0.5MPa.
Fig. 15a shows a cover 37 for a stacked apparatus 23 according to the invention. The cap 37 comprises an end plate 33, for example an upper end plate 38, which is connected to two dispensing caps 41, wherein one dispensing cap 41 comprises a water connection 39 for introducing liquid and the other dispensing cap 41 comprises a water outlet 40 for discharging liquid.
Fig. 15b shows the cover 37 of the stacked apparatus 23 with the dispensing cover 41 removed, so that the liquid dispensing space in the end plate 42 and the I-channels 14 connected to the liquid dispensing space in the end plate 42 are visible in the end plate 33.
Fig. 15c shows a water diverter cover 41 for a cover 37 of a stacked apparatus 23 according to the invention, wherein the water diversion space in the water diverter cover 43 is visible.
Fig. 15d shows a schematic view of a simulated water distribution in the cover 37 according to the invention. The figure also shows the different points of the cap 37 and the different flow rates to the transition region of the type I channel 14.
Fig. 16 shows an anode frame 7 on which the type I channels 14 and type II channels 15 are arranged, as well as the area coated with the sealing material coating 22 and the area coated with the sealing material 'coating 22' and having a reduced coating thickness. The type II channel 15 connects a portion of the type I channel 14 with the first opening 6. They are arranged at intervals along the first side 27 of the first opening and the third side 29 of the first opening, so that each of the type II channels 15 is able to introduce water or water and gas into the same area or active area of the first opening 6.
Fig. 16a to c show an enlarged portion of the anode frame in fig. 16.
Fig. 17 shows a cathode frame 11 in which the type I channels 14 and type II channels 15 are arranged, as well as the region with the sealing material coating 22 and the region with the sealing material coating 22″ and with a reduced layer thickness. The type II channel 15 connects a part of the type I channel 14 with the second opening 9. They are arranged at intervals along the second side 28 'of the second opening and the fourth side 30' of the second opening, so that each of the type II channels 15 introduces water or water and gas into the same area or active area of the first opening 6.
Claims (21)
1. Frame (1) for an electrochemical cell (2) of a stacked device (23), the frame (1) comprising a first side (4) of the frame, a second side (5) of the frame, an anode frame (8) and a cathode frame (11), the first side (4) of the frame having a planar first surface, the second side (5) of the frame being opposite the first side (4) and having a planar second surface, and
Wherein the anode frame comprises a first side (4) of the frame, a side (4 ') opposite the first side (4) of the frame of the anode frame, and a first opening (6) for receiving an anode (7), wherein the first opening (6) extends from the first side (4) of the frame to the opposite side (4') of the anode frame,
Wherein the cathode frame (11) comprises a second side (5) of the frame, a side (5 ') opposite the second side (5) of the frame of the cathode frame, and a second opening (9) for receiving the cathode (10), wherein the second opening (9) extends from the second side (5) of the frame to the opposite side (5') of the cathode frame,
Wherein a side (4 ') opposite to a first side (4') of the frame of the anode frame and a side (5 ') opposite to a second side (5') of the frame of the cathode frame are arranged adjacent,
Wherein the anode frame (8) and the cathode frame (11) are connected with each other,
Wherein the first opening (6) and the second opening (11) are connected to each other,
Characterized in that the first opening (6) is larger than the second opening (9), wherein the anode frame (8) and the cathode frame (11) are arranged such that a side (4 ') opposite to the first side (4) of the frame of the anode frame and a side (5') opposite to the second side (5) of the frame of the cathode frame form a step (12) at the transition from the anode frame (8) to the cathode frame (11), wherein the step (12) forms a planar third surface, which planar third surface acts as a support surface for a solid electrolyte, such as a membrane (13), and wherein the anode frame (8) comprises a core (21) and a sealing material coating (22), and wherein the cathode frame (11) comprises a core (21) and a sealing material coating (22).
2. Frame (1) according to claim 1, comprising one or more type I channels (14) and comprising one or more type II channels (15), said type I channels (14) being used for inputting and outputting liquids and gases, said type II channels (15) being used for inputting and outputting liquids and gases, wherein the type I channels (14) are not connected to the first opening (6) of the anode frame (8) or to the second opening (9) of the cathode frame (11), and wherein the type II channels (15) connect the type I channels (14) to the first opening (6) and to the second opening (9), characterized in that the anode frame (8) comprises one or more type II channels (15) on the surface of the first side (4) of the frame, said one or more type II channels (15) being connected to the one or more type I channels (14) and connecting the one or more type I channels (14) to the first opening (6), and wherein the type II channels (15) are not arranged in the opposite direction of the side (4) of the frame (4) (I channels (15) when the frame (1) is mounted in the electrochemical cell (2) or the stack (23).
3. Frame (1) according to claim 1 or 2, comprising one or more type I channels (14) for the input and output of liquids and gases, and one or more type II channels (15) for the input and output of liquids and gases, wherein the type I channels (14) are not connected to the first opening (6) of the anode frame (8) or to the second opening (9) of the cathode frame (11), and wherein the type II channels (15) connect the type I channels (14) to the second opening (9) and to the first opening (6), characterized in that the cathode frame (11) comprises one or more type II channels (15) on the surface of the second side (5) of the frame, said one or more type II channels (15) being connected to the one or more type I channels (14) and connecting the type I channels (14) to the second opening (9), and wherein the one or more type II channels (15) are arranged in the opposite direction of the second side (5) of the frame (5) than the bipolar plate (15) when the frame (1) is mounted in the electrochemical cell (2) or the stacked device (23).
4. A frame (1) according to any one of claims 2 or 3, wherein the first opening (6) is formed by a first side (27), a second side (28), a third side (29) and a fourth side (30), and wherein, in order to allow a liquid to flow uniformly through the first opening (6) and to continuously remove reaction heat from the first opening (6), each of the type I channels (14) connected to the first opening (6) is connected to the first opening (6) by at least two type II channels (15), and
The II-type channels (15) are arranged adjacent to each other on the first side (4) of the frame, and the distance between two adjacent II-type channels (15) on the first side (27) of the first opening is less than or equal to 3mm, and the distance between two adjacent II-type channels (15) on the third side (29) of the first opening is less than or equal to 3mm.
5. Frame (1) according to any one of claims 2 to 4, wherein the second opening (9) is formed by a first side (27 '), a second side (28'), a third side (29 ') and a fourth side (30'), and each I-channel (14) connected to the second opening (9) is connected to the second opening (9) by at least two II-channels (15) in order to make the water flow uniform through the second opening (9) and to continue the discharge of the reaction heat from the second opening (9), and
The II-type channels (15) are arranged adjacent to each other on the second side (5) of the frame, and the distance between two adjacent II-type channels (15) on the second side (28 ') of the second opening is less than or equal to 3mm, and the distance between two adjacent II-type channels (15) on the fourth side (30') of the second opening is less than or equal to 3mm.
6. Frame (1) according to any one of claims 4 and 5, wherein the distance between adjacent type II channels (15) at the first side (27) of the first opening and adjacent type II channels (15) at the third side (29) of the first opening is equal, and wherein optionally the distance between adjacent type II channels (15) at the second side (28 ') of the second opening and adjacent type II channels (15) at the fourth side (30') of the second opening is equal.
7. Frame (1) according to any one of claims 4 to 6, wherein at least two type II channels (15) between a first side (27) of the first opening and a type I channel (14) connected to the first opening (6) by means of the at least two type II channels (15) are arranged in a fan-like manner, wherein at least two type II channels (15) between a third side (29) of the first opening and a type I channel (14) connected to the first opening (6) by means of the at least two type II channels (15) are arranged in a fan-like manner, and wherein optionally at least two type II channels (15) between a second side (28 ') of the second opening and a type I channel (14) connected to the second opening (9) by means of the at least two type II channels (15) are arranged in a fan-like manner, and optionally at least two type II channels (15) between a fourth side (30') of the second opening and a type I channel (14) connected to the second opening (9) by means of the at least two type II channels (15) are arranged in a fan-like manner.
8. Frame (1) according to any one of the preceding claims, wherein the core (21) of the anode frame (8) is made of metal and the core of the cathode frame (11) is made of metal, and wherein the sealing material coating (22) comprised by the anode frame (8) is a rubber coating and the sealing material coating (22) comprised by the cathode frame (11) is a rubber coating.
9. Frame (1) according to any of the preceding claims, wherein the sealing material coating (22) of the anode frame (8) has a part of the sealing material coating (22 ") with a reduced layer thickness compared to the layer thickness of the sealing material coating (22) in order to reduce the contact pressure, and/or wherein the sealing material coating (22) of the cathode frame (11) has a part of the sealing material coating (22") with a reduced layer thickness compared to the layer thickness of the sealing material coating (22) in order to reduce the contact pressure.
10. Frame (1) according to claim 9, wherein a part of the sealing material coating (22) of the anode frame (8) has an annular protrusion 26 "to increase the sealing effect, wherein the annular protrusion 26" surrounds the first opening 6, and/or wherein a part of the sealing material coating (22) of the cathode frame (11) has an annular protrusion 26 "to increase the sealing effect, wherein the annular protrusion 26" surrounds the second opening 9.
11. Frame (1) according to any one of the preceding claims, wherein the anode frame (8) comprises one or more connection elements for connection with the cathode frame (11), such as one or more pins (19), and the cathode frame (11) comprises one or more connection elements for connection with the anode frame (8), such as one or more holes (18), wherein the arrangement of the connection elements enables the anode frame (8) and the cathode frame (11) to be connected to each other, such as the arrangement of the pins (19) and the holes (18) enables the insertion of one or more holes (18) in the cathode frame (11) into one or more pins (19) in the anode frame (8), thereby enabling the anode frame (8) and the cathode frame (11) to be connected to each other.
12. Electrochemical cell (2) for operation and conversion or generation of high pressure liquid or gas under a pressure difference of up to 40 bar, comprising a solid electrolyte, such as a membrane (13), an anode (7), a cathode (10), characterized in that the electrochemical cell (2) comprises a frame (1) according to any of claims 1 to 11, wherein the first opening (6) of the anode frame (8) comprises the anode (7) and the second opening (9) of the cathode frame (11) comprises the cathode (10), wherein the solid electrolyte, such as the membrane (13), is arranged between a side (4 ") opposite to the first side of the frame of the anode frame and a side (5") opposite to the second side of the frame of the cathode frame, wherein one side of the solid electrolyte, such as the membrane (13), rests on the anode (7) and the other side of the solid electrolyte, such as the membrane (13), rests on the step (12) and the cathode (10).
13. Electrochemical cell (2) according to claim 12, characterized in that the thickness of the solid electrolyte, such as the membrane (13), is less than 80 μm, such as less than 50 μm, preferably less than 20 μm or less.
14. A preassembled module (20) for producing a stacked device (23) for electrochemical conversion or generation of gases and liquids under pressure, comprising an anode frame (8), a cathode frame (11), a BPP (16), an anode (7) and a cathode (10),
Wherein the anode frame (8) comprises a first side (4) of the frame having a planar first surface, a side (4') opposite to the first side (4) of the frame of the anode frame, and a first opening (6) for receiving the anode (7),
Wherein the first opening (6) extends from a first side (4) of the frame to a side (4') opposite to the first side (4) of the frame of the anode frame, wherein the first opening (6) is surrounded by the anode frame (8) and the anode frame (8) comprises at least one connecting element, preferably a pin (19), for connection with the cathode frame (11),
Wherein the cathode frame (11) comprises a second side (5) of the frame having a planar second surface, a side (5') opposite to the second side (5) of the frame of the cathode frame, and a second opening (9) for receiving the cathode (10),
Wherein the second opening (9) extends from the second side (5) of the frame to a side (5') opposite to the second side (5) of the frame of the cathode frame and is surrounded by the cathode frame (10), the cathode frame (11) comprising at least one connecting element for connection with the anode frame (8), preferably a hole (18) for receiving a pin (19),
Wherein the BPP (16) is arranged between the first side (4) of the frame and the second side (5) of the frame,
Characterized in that the anode frame (8) comprises a core (21), preferably made of metal or plastic, and a sealing material coating (22), wherein the sealing material coating (22) is preferably a coating made of rubber, and
Wherein the BPP (16) is connected to the anode (7) to form a BPP/anode (36), and wherein the BPP/anode (36) is inserted or pressed into the first opening (6) and surrounded by the anode frame (8),
The cathode frame (10) comprises a core (21), preferably metal or plastic, and comprises a sealing material coating (22), preferably a rubber coating, wherein the cathode (10) is inserted or pressed into the second opening (9) and surrounded by the cathode frame (11), wherein the connecting elements of the anode frame (8) are connected with the connecting elements of the cathode frame (11), preferably at least one pin (19) is inserted into at least one hole (18) such that the anode frame (8) and the cathode frame (11) are connected to each other,
Wherein the first opening (6) is larger than the second opening (9), the arrangement of the anode frame (8) and the cathode frame (11) is such that the first side (4) of the frame and the second side (5) of the frame form a step (12) at the transition from the anode frame (8) to the cathode frame (11), wherein the step (12) forms a planar third surface which acts as a support surface for the solid electrolyte, for example for the membrane (13), wherein one side of the BPP (16) rests on the anode (7) and the anode frame (8) and the other side of the BPP (16) rests on the cathode (10), the cathode frame (11) and the step (12).
15. Method for manufacturing a pre-assembled module (20) for a stacked device (23) for electrochemical conversion or generation of gases and liquids under pressure, comprising the steps of:
a) -making a core (21) of metal for an anode frame (8), wherein the core (21) comprises a first side (4) of the frame having a planar first surface and a side (4 ") opposite to the first side (4) of the frame of the anode frame, wherein the first side (4) of the frame and the side (4") opposite to the first side (4) of the frame of the anode frame comprise a first opening (6), said first opening (6) extending from the first side (4) of the frame to the side (4 ") opposite to the first side (4) of the frame of the anode frame and being framed by the anode frame (8), and forming one or more I-channels (14) for inputting and outputting liquid and gas in the anode frame (8), wherein said I-channels (14) are not connected to the first opening (6) in the anode frame (8), and the anode frame (8) comprises at least one connecting element, preferably at least one pin (19), for connection to the cathode frame (11),
B) All or part of the surface of the metal core (21) produced according to a), preferably at least 90% of the surface of the metal core (21) of the anode frame (8) produced according to a), is coated with rubber by means of a vulcanization process, said surface being coated wholly or partly with natural rubber or synthetic rubber and subsequently vulcanized, whereby a rubber-made coating (22) is formed on the metal core (21), wherein in the rubber-made coating one or more type II channels (15) are formed on the surface of the first side (4), which type II channels (15) are connected to one or more type I channels (14) and connect the type I channels (14) to the first opening (6), and said one or more type II channels (15) are arranged in the direction of the BPP (16) when the anode frame (8) is mounted in the electrochemical cell (2) or the stacked device (23), wherein in the rubber-made coating, in the side (4 ") opposite to the type II channels (4"), which are not formed in the first side (4 "), of the anode frame (4'),
C) Placing or pressing an anode (7) into an anode frame (8) produced according to a) and b), preferably the PTL anode (7) is connected with a BPP (16) to form a BPP/PTL anode (36),
D) -making a core (21) of metal for a cathode frame (11), wherein the core (21) comprises a second side (5) with a planar second surface and a side (5 ") opposite to the second side (5) of the cathode frame, wherein the second side (5) and the side (5") opposite to the second side (5) of the cathode frame comprise a second opening (9), which second opening (9) extends from the second side (5) of the frame to the side (5 ") opposite to the second side (5) of the cathode frame and is framed by the cathode frame (11), wherein one or more I-channels (14) for inputting and outputting liquid and gas are provided in the cathode frame (11), wherein the I-channels (14) are not connected to the second opening (9) in the cathode frame (11), wherein the cathode frame (11) comprises at least one connecting element, such as at least one hole (18), for connecting with the anode frame (8),
E) All or part of the surface of the core (21) made of metal produced according to d) for the cathode frame (11), preferably at least 90% of the surface of the core (21) produced according to d) for forming a rubber coating by vulcanization, said surface being entirely or partly coated with natural rubber or synthetic rubber and subsequently vulcanized, whereby a coating made of rubber is formed on the core (21) made of metal as a sealing material coating (22), wherein in the coating made of rubber one or more type II channels (15) are formed on the surface of the second side (5) of the frame, said one or more type II channels (15) being connected to one or more type I channels (14) and connecting the type I channels (14) to the second opening (9), and said one or more type II channels (15) are arranged in the direction of the BPP (16) and in the coating made of rubber in the direction of the electrochemical cell (2) or the stacked device (23) in the side (5 ') opposite to the second side (5') of the cathode frame (5),
F) The cathode frame (11) produced according to d) and e) is connected to the anode frame (8) produced according to a) to c) by means of at least one connecting element, preferably at least one hole (19), of the cathode frame (11) and by means of at least one connecting element, preferably at least one pin (18), of the anode frame (8), preferably at least one hole (19) being slipped over at least one pin (18), whereby the cathode frame (11) is connected to the anode frame (8), wherein the BPP (16) is arranged between the first side (4) of the frame and the second side (5) of the frame, and the cathode (10) is inserted or pressed into the cathode frame (11).
16. A method of manufacturing a stacked device (23) operating under a pressure differential to convert or generate a high pressure liquid or gas, the method comprising the steps of:
a) Stacking at least x preassembled modules (20) according to claim 14 or at least x preassembled modules (20) produced according to claim 15 and at least x+1 solid electrolytes together, for example together with at least x+1 membranes (13), one above the other, wherein a stack (3) of preassembled modules is produced, wherein in the stack (3) of preassembled modules one preassembled module (20) and one solid electrolyte, for example membrane (13), are stacked alternately one above the other, and wherein one solid electrolyte, for example membrane (13), is arranged between each two adjacent preassembled modules (20), and wherein one solid electrolyte is arranged between the top side and the bottom side of the stack (3) of preassembled modules, respectively, and
B) A half-cell anode, preferably a single anode (7 ') and an anode frame (8), is arranged parallel to an external solid electrolyte, such as an external membrane (13), on one side of the stack (3) of pre-assembled modules, and a half-cell cathode, preferably a single cathode (10') and a cathode frame (11), is arranged parallel to an external solid electrolyte, such as an external membrane (13), on the other side of the stack (3) of pre-assembled modules,
C) The end plates (33) are arranged parallel to the half-cell anode and parallel to the half-cell cathode, and the resulting stack is then compressed between the two end plates (33) to form a stacked arrangement (23),
Wherein x is an integer and is not less than 2.
17. Stacked device (23) for operation under pressure differential to convert or generate high pressure liquid or gas, comprising x pre-assembled modules (20) according to claim 14 or x pre-assembled modules (20) produced according to claim 15, x+1 solid electrolytes (e.g. x+1 membranes (13)), single anode (7 ') or half-unit anode, single cathode (10') or half-unit cathode and two end plates (33), wherein x pre-assembled modules (20) and x+1 solid electrolytes (e.g. x+1 membranes (13)) are stacked one above the other to form a stack (3) of pre-assembled modules, wherein one pre-assembled module (20) and one solid electrolyte (e.g. membrane (13)) are stacked one above the other in a stack (3) of pre-assembled modules, and
Wherein a solid electrolyte, such as a membrane (13), is arranged between each two adjacent pre-assembled modules (20), respectively arranged on the top side and the bottom side of the stack (3) of pre-assembled modules, and
A single anode (7 ') or a half-cell anode is arranged parallel to an external solid electrolyte, such as an external membrane (13), on one side of the stack (3) of pre-assembled modules, a single cathode (10') or a half-cell cathode is arranged parallel to an external solid electrolyte, such as an external membrane (13), on the other side of the stack (3) of pre-assembled modules,
Wherein end plates (33) are arranged parallel to the individual anodes (7 ') or half-cell anodes and parallel to the individual cathodes (10') or half-cell cathodes, respectively, and the resulting stack is compressed between the two end plates (33) to form a stacked arrangement (23),
Wherein x is an integer and is not less than 2.
18. Stacked device (23) for operation under pressure differential to generate high pressure liquid or gas, comprising x+1 electrochemical cells (2) according to claim 12 or 13, comprising x+1 solid electrolytes, such as x+1 membranes (13) and x-1 BPPs (16), an upper end plate (38) and a lower end plate (44),
Wherein x+1 electrochemical cells (2) and x-1 BPPs (16) are alternately stacked, in which stack one electrochemical cell (2) and one BPP (16) are alternately stacked, and wherein one BPP (16) is arranged at the top side and the bottom side of the stack, respectively, one BPP (16) is also arranged between every two adjacent electrochemical cells (2), and
Wherein the upper end plate (38) is arranged parallel to the BPP (16) on the upper side of the stack, the lower end plate (44) is arranged parallel to the BPP (16) on the lower side of the stack, and the resulting stack is compressed between the upper end plate (38) and the lower end plate (44) to form a stacked arrangement (23),
Wherein x is an integer and is not less than 2.
19. The stacked device (23) according to any one of claims 17 or 18 or the stacked device (23) produced according to claim 16, wherein the thickness of each x+1 solid electrolyte in the stacked device (23), e.g. the thickness of each x+1 film (13) in the stacked device (23), is less than 50 μιη, preferably 20 μιη or less.
20. Stacked device (23) according to any one of claims 17 to 19 or a manufactured stacked device (23) according to claim 16, comprising two end plates (33), wherein preferably an upper end plate (38) is arranged at the upper side of the stack and a lower end plate (44) is arranged at the lower side of the stack, wherein preferably the upper end plate (38) comprises at least one water connection (39) for introducing liquid, at least one drain opening (40) for draining liquid and at least two dispensing caps (41), wherein at least two spaces for dispensing liquid are present in at least one end plate (33) for providing a liquid space, and wherein each of the at least two dispensing caps (41) has a space for dispensing liquid in each dispensing cap (43), and wherein the at least one dispensing cap (43) for introducing liquid into the stacked device (23) is connected to the at least one water connection (39) for introducing liquid and the space for dispensing liquid in the end plate (42), and wherein the at least one dispensing cap (43) is connected to the other dispensing cap (42) for draining liquid from the stacked device (23).
21. Cover 37 of a stacked device 23 according to any of claims 17-19, wherein the end plate (33), for example the upper end plate (38), comprises at least one water connection (39) for introducing liquid into the stacked device (23), at least one drain opening (40) for draining liquid out of the stacked device (23) and at least two distribution covers (41), wherein the end plate (33) has at least two spaces for distributing liquid in the end plate (33) to provide a liquid space, wherein each distribution cover (43) of the at least two distribution covers (41) has a space for distributing liquid, wherein the at least one distribution cover (43) is connected to at least one liquid distribution space for introducing liquid into the water connection (39) of the stacked device (23) and into the end plate (33), and wherein the at least one other distribution cover (43) is connected to the at least one liquid distribution space for draining liquid out of the stacked device (23) and into the end plate (33) for draining liquid out of the stacked device (23) and the liquid distribution space in the end plate (33) from the stacked device (23).
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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EP21202604.1 | 2021-10-14 | ||
EP22162709.4 | 2022-03-17 | ||
EP22170349 | 2022-04-27 | ||
EP22170349.9 | 2022-04-27 | ||
PCT/EP2022/078416 WO2023062088A2 (en) | 2021-10-14 | 2022-10-12 | Frame for electrochemical cells and stack-type devices |
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Publication Number | Publication Date |
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CN118119737A true CN118119737A (en) | 2024-05-31 |
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CN202280069261.1A Pending CN118119737A (en) | 2021-10-14 | 2022-10-12 | Electrochemical cell and frame for stacked device |
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CN (1) | CN118119737A (en) |
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2022
- 2022-10-12 CN CN202280069261.1A patent/CN118119737A/en active Pending
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