CA2701366A1 - Electrochemical system with fluid bypassing limitation elements - Google Patents
Electrochemical system with fluid bypassing limitation elements Download PDFInfo
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- CA2701366A1 CA2701366A1 CA2701366A CA2701366A CA2701366A1 CA 2701366 A1 CA2701366 A1 CA 2701366A1 CA 2701366 A CA2701366 A CA 2701366A CA 2701366 A CA2701366 A CA 2701366A CA 2701366 A1 CA2701366 A1 CA 2701366A1
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- boundary wall
- bipolar plate
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- 239000012530 fluid Substances 0.000 title claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 24
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000011324 bead Substances 0.000 claims description 17
- 230000006835 compression Effects 0.000 claims description 11
- 238000007906 compression Methods 0.000 claims description 11
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 6
- 239000011796 hollow space material Substances 0.000 claims description 6
- 238000004049 embossing Methods 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 23
- 239000000446 fuel Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 239000012809 cooling fluid Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/036—Bipolar electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Fuel Cell (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention describes an electrochemical system as well as a bipolar plate for use in an electrochemical system. The electrochemical system (1), consists of a layering of several cells (2), which in each case are separated from one another by bipolar plates (3), wherein the bipolar plates comprise openings for the cooling (4) or for the removal and supply of operating media (5) to the cells, and the layering may be set under mechanical compressive stress, wherein at least one cell comprises an electrochemically active region (6) which is surrounded by a boundary wall (7) of the bipolar plate, and a channel structure (8) of the bipolar plate is provided within the electrochemically active region, for the uniform media distribution, wherein at least one gas diffusion layer (9) is provided for the micro-distribution of media.
Limitation elements (10) are provided in the border region between the channel structure as well as the boundary wall, for avoiding fluid from bypassing between the channel structure and the boundary wall, wherein the gas diffusion layer covers the channel structure and/or at least parts of the limitation elements. The reliability and the efficiency of electrochemical systems are decisively increased by way of preventing the bypass in the border region of the electrochemically active field.
Limitation elements (10) are provided in the border region between the channel structure as well as the boundary wall, for avoiding fluid from bypassing between the channel structure and the boundary wall, wherein the gas diffusion layer covers the channel structure and/or at least parts of the limitation elements. The reliability and the efficiency of electrochemical systems are decisively increased by way of preventing the bypass in the border region of the electrochemically active field.
Description
Electrochemical system The present invention relates to an electrochemical system, as well as to a bipolar plate for use in such a system.
The electrochemical system may for example be a fuel cell system or an electrochemical compressor system, in particular an electrolyser with which, by way of applying a potential, apart from the production of hydrogen and oxygen from water, these gases are simultaneously compressed under pressure. Apart from this, electrochemical compressor systems such as electrochemical hydrogen compressors are also known, to which gaseous, molecular hydrogen is supplied and in which this is electrochemically compressed by applying a potential. This electrochemical compressing lends itself in particular for small quantities of hydrogen to be compressed, since a mechanical compression of the hydrogen here would require significantly more effort.
Electrochemical systems are known, with which an electrochemical cell stack is constructed with a layering of several electrochemical cells, which in each case are separated from one another by bipolar plates. With this, the bipolar plates have several tasks:
- the electrical contacting of the electrodes of the individual electrochemical cells (e.g. fuel cells) and conveying the current further to the adjacent cell (series connection of the cells), - the supply of the cells with media, i.e. reaction gases, and the removal of reaction products via a channel structure, which is arranged in an electrochemically active region (gas distribution structure/flowfield), - the further conveying the waste heat arising during the reaction in the electrochemical cell, as well as - the sealing of the different media channels or cooling channels against one another and to the outside.
For the supply and removal of media from the bipolar plates to the actual electrochemical cells, these e.g. are MEAs (membrane electrode assembly) with a gas diffusion layer in each case orientated towards the bipolar plates (e.g. of a metal non-woven or carbon non-woven), and the bipolar plates may have openings for cooling, or for the supply and removal of media.
The electrochemical system may for example be a fuel cell system or an electrochemical compressor system, in particular an electrolyser with which, by way of applying a potential, apart from the production of hydrogen and oxygen from water, these gases are simultaneously compressed under pressure. Apart from this, electrochemical compressor systems such as electrochemical hydrogen compressors are also known, to which gaseous, molecular hydrogen is supplied and in which this is electrochemically compressed by applying a potential. This electrochemical compressing lends itself in particular for small quantities of hydrogen to be compressed, since a mechanical compression of the hydrogen here would require significantly more effort.
Electrochemical systems are known, with which an electrochemical cell stack is constructed with a layering of several electrochemical cells, which in each case are separated from one another by bipolar plates. With this, the bipolar plates have several tasks:
- the electrical contacting of the electrodes of the individual electrochemical cells (e.g. fuel cells) and conveying the current further to the adjacent cell (series connection of the cells), - the supply of the cells with media, i.e. reaction gases, and the removal of reaction products via a channel structure, which is arranged in an electrochemically active region (gas distribution structure/flowfield), - the further conveying the waste heat arising during the reaction in the electrochemical cell, as well as - the sealing of the different media channels or cooling channels against one another and to the outside.
For the supply and removal of media from the bipolar plates to the actual electrochemical cells, these e.g. are MEAs (membrane electrode assembly) with a gas diffusion layer in each case orientated towards the bipolar plates (e.g. of a metal non-woven or carbon non-woven), and the bipolar plates may have openings for cooling, or for the supply and removal of media.
2 PCT/EP2008/008540 With known bipolar plates, the gas distribution along the MEA or the gas diffusion layer is effected via channel structures or meander structures on both sides of the bipolar plate.
It is known, in particular for metallic bipolar plates, to stamp channel structures into these bipolar plates and thereby also to stamp a boundary wall at the same time unitary with the bipolar plate, which surrounds the electrochemically active region. The boundary wall thereby often has a bead-like shaping. Now it has been found in series of trials that such bipolar plates may display large fluctuations with regard to their performance, which appear to originate from an insufficient distribution of media.
It is therefore the object of the present invention to provide an electrochemical system or a bipolar plate which do not have fluctuations of performance due to insufficient distribution of media in the electrochemically active region.
This object is achieved by the subject-matters of the independent claims.
Firstly, this is an electrochemical system consisting of a layering of several cells which are in each case separated from one another by bipolar plates, wherein the bipolar plates comprise openings for cooling or for the removal and supply of media to the cells, and the layering may be set under mechanical compressive stress, wherein at least one cell comprises an electrochemically active region which is surrounded by a boundary wall of the bipolar plate, and a channel structure of the bipolar plate for the uniform distribution of media is provided within the electrochemically active region, wherein at least one gas diffusion layer is provided for micro-distribution of the medium. Limitation elements are provided in the border region between the channel structure as well as the boundary wall, for avoiding media flow between the channel structure and the boundary wall. Thereby, the gas diffusion layer covers the channel structure and/or at least parts of the limitation elements.
The bipolar plate for use in an electrochemical system according to the invention is characterised in that this bipolar plate has a base plane, and a channel structure (flowfield) projecting from this base plane, as well as openings for the supply and removal of media are provided, and the channel structure as well as the openings are surrounded by a boundary wall (under certain circumstances provided with openings for leading through fluid) and that at least one limitation element for preventing media bypassing in the border region between the boundary wall and the channel structure is provided in the region between the boundary wall and the outer edge of the channel structure.
Thus a bypass of media at the channel structure is largely prevented with the limitation elements according to the invention. A uniform distribution of media over the channel structure
It is known, in particular for metallic bipolar plates, to stamp channel structures into these bipolar plates and thereby also to stamp a boundary wall at the same time unitary with the bipolar plate, which surrounds the electrochemically active region. The boundary wall thereby often has a bead-like shaping. Now it has been found in series of trials that such bipolar plates may display large fluctuations with regard to their performance, which appear to originate from an insufficient distribution of media.
It is therefore the object of the present invention to provide an electrochemical system or a bipolar plate which do not have fluctuations of performance due to insufficient distribution of media in the electrochemically active region.
This object is achieved by the subject-matters of the independent claims.
Firstly, this is an electrochemical system consisting of a layering of several cells which are in each case separated from one another by bipolar plates, wherein the bipolar plates comprise openings for cooling or for the removal and supply of media to the cells, and the layering may be set under mechanical compressive stress, wherein at least one cell comprises an electrochemically active region which is surrounded by a boundary wall of the bipolar plate, and a channel structure of the bipolar plate for the uniform distribution of media is provided within the electrochemically active region, wherein at least one gas diffusion layer is provided for micro-distribution of the medium. Limitation elements are provided in the border region between the channel structure as well as the boundary wall, for avoiding media flow between the channel structure and the boundary wall. Thereby, the gas diffusion layer covers the channel structure and/or at least parts of the limitation elements.
The bipolar plate for use in an electrochemical system according to the invention is characterised in that this bipolar plate has a base plane, and a channel structure (flowfield) projecting from this base plane, as well as openings for the supply and removal of media are provided, and the channel structure as well as the openings are surrounded by a boundary wall (under certain circumstances provided with openings for leading through fluid) and that at least one limitation element for preventing media bypassing in the border region between the boundary wall and the channel structure is provided in the region between the boundary wall and the outer edge of the channel structure.
Thus a bypass of media at the channel structure is largely prevented with the limitation elements according to the invention. A uniform distribution of media over the channel structure
3 PCT/EP2008/008540 is achieved by way of this, and the undesired performance fluctuations are eliminated in this manner.
Thereby, it is particularly advantageous if the gas diffusion layer not only covers the channel structure, but also at least parts of the limitation elements. On account of this, an additional compression of the gas diffusion layer occurs in this region, which is greater than the compression in the region of the "normal" channel structure. Thus a bypass of medium in the questionable region between the channel structure and the boundary wall is therefore prevented in an even greater manner.
Advantageous further embodiments of the present invention are described in the dependent claims.
One advantageous further embodiment envisages the height of the limitation elements being selected in a manner such that the compression of the gas diffusion layer in the contact region to the limitation elements being greater than in the contact region to the channel structure.
Thus a particularly good sealing in this border region is achieved. A further advantageous embodiment envisages the limitation elements being designed as extensions of the channel structure, which merge into the boundary walls. This is particularly advantageous with metallic bipolar plates, since thus a combined and unitary embossing of the limitation elements and elements of the channel structure is possible. Basically, it is possible to provide one or more limitation elements. With several limitation elements, these are preferably distanced to one another and particularly preferably here two adjacent limitation elements together with the boundary wall in each case form chambers between the channel structure and the boundary wall, so that bulkheads are formed (as with a freight ship), in order to prevent the bypass as securely as possible.
The repetition distance of individual limitation elements thereby is preferably greater than 2 mm, particularly preferably greater than 5 - 10 mm (with smaller distances, the boundary wall would be mechanically weakened far too much). As an alternative, one could also say that here at least one limitation element is to be provided for 100 mm length of the boundary wall, preferably five to twenty five limitation elements. One further advantageous design envisages the boundary wall running in a serpentine manner, thus making the boundary wall mechanically stronger. With a serpentine course of the boundary wall, in each case the portion of the boundary wall which lies closest to the channel structure may be connected to the channel structure via a limitation element.
It is advantageous, with regard to the limitation elements which are to prevent the bypass between the boundary wall and the channel structure, for these to run essentially transversely to
Thereby, it is particularly advantageous if the gas diffusion layer not only covers the channel structure, but also at least parts of the limitation elements. On account of this, an additional compression of the gas diffusion layer occurs in this region, which is greater than the compression in the region of the "normal" channel structure. Thus a bypass of medium in the questionable region between the channel structure and the boundary wall is therefore prevented in an even greater manner.
Advantageous further embodiments of the present invention are described in the dependent claims.
One advantageous further embodiment envisages the height of the limitation elements being selected in a manner such that the compression of the gas diffusion layer in the contact region to the limitation elements being greater than in the contact region to the channel structure.
Thus a particularly good sealing in this border region is achieved. A further advantageous embodiment envisages the limitation elements being designed as extensions of the channel structure, which merge into the boundary walls. This is particularly advantageous with metallic bipolar plates, since thus a combined and unitary embossing of the limitation elements and elements of the channel structure is possible. Basically, it is possible to provide one or more limitation elements. With several limitation elements, these are preferably distanced to one another and particularly preferably here two adjacent limitation elements together with the boundary wall in each case form chambers between the channel structure and the boundary wall, so that bulkheads are formed (as with a freight ship), in order to prevent the bypass as securely as possible.
The repetition distance of individual limitation elements thereby is preferably greater than 2 mm, particularly preferably greater than 5 - 10 mm (with smaller distances, the boundary wall would be mechanically weakened far too much). As an alternative, one could also say that here at least one limitation element is to be provided for 100 mm length of the boundary wall, preferably five to twenty five limitation elements. One further advantageous design envisages the boundary wall running in a serpentine manner, thus making the boundary wall mechanically stronger. With a serpentine course of the boundary wall, in each case the portion of the boundary wall which lies closest to the channel structure may be connected to the channel structure via a limitation element.
It is advantageous, with regard to the limitation elements which are to prevent the bypass between the boundary wall and the channel structure, for these to run essentially transversely to
4 PCT/EP2008/008540 the boundary wall as well as essentially transversely to the outermost elements of the channel structure.
The constructional shape of the limitation elements is moreover dependent on the respective design of the channel structures. If the channel structures for example are provided as individual elements, then the limitation elements may also be provided in a linear manner, in order to avoid a bypass. In the other case, these limitation elements are also to be provided as individual elements.
A further advantageous embodiment envisages the boundary wall having a greater height with respect to a base plane of the bipolar plate, than the predominant elevation of the channel structure in the vicinity of the boundary wall with respect to this base plane. Vicinity hereby is to be understood as a distance to the boundary wall of maximal 1 cm.
The limitation elements of the bipolar plate should at least have the height of the predominant elevation of the channel structure starting from the base plane.
This means that they should therefore preferably have the same height as the channel structure or have a height between the height of the channel structure and the height of the boundary wall.
The limitation elements are preferably provided as embossings in a (preferably metallic) bipolar plate.
A further advantageous design envisages a bipolar plate being constructed of two plates, wherein the at least one limitation element is hollow on the side of the first plate which is distant to the electrochemically active side, and this hollow space acts as a complementary space for inserting the second plate of the bipolar plate.
The boundary walls preferably have the shape of a bead, in particular a full bead or a half bead and thus are an integral component which is unitary with the bipolar plate, but however attachment parts are also possible here.
One particularly advantageous embodiment envisages the openings of the bipolar plate for cooling or for the removal or supply of media, being provided with elastic bead arrangements, wherein these bead arrangements comprise openings for conducting fluid or gaseous media into a hollow space of the bipolar plate, or to the electrochemically active region.
Preferably, the conducting of media through the electrochemically active region is effected in a manner such that the location of the introduction of the medium and the location of the leading-out of the medium is effected at respective maximally distanced points of the
The constructional shape of the limitation elements is moreover dependent on the respective design of the channel structures. If the channel structures for example are provided as individual elements, then the limitation elements may also be provided in a linear manner, in order to avoid a bypass. In the other case, these limitation elements are also to be provided as individual elements.
A further advantageous embodiment envisages the boundary wall having a greater height with respect to a base plane of the bipolar plate, than the predominant elevation of the channel structure in the vicinity of the boundary wall with respect to this base plane. Vicinity hereby is to be understood as a distance to the boundary wall of maximal 1 cm.
The limitation elements of the bipolar plate should at least have the height of the predominant elevation of the channel structure starting from the base plane.
This means that they should therefore preferably have the same height as the channel structure or have a height between the height of the channel structure and the height of the boundary wall.
The limitation elements are preferably provided as embossings in a (preferably metallic) bipolar plate.
A further advantageous design envisages a bipolar plate being constructed of two plates, wherein the at least one limitation element is hollow on the side of the first plate which is distant to the electrochemically active side, and this hollow space acts as a complementary space for inserting the second plate of the bipolar plate.
The boundary walls preferably have the shape of a bead, in particular a full bead or a half bead and thus are an integral component which is unitary with the bipolar plate, but however attachment parts are also possible here.
One particularly advantageous embodiment envisages the openings of the bipolar plate for cooling or for the removal or supply of media, being provided with elastic bead arrangements, wherein these bead arrangements comprise openings for conducting fluid or gaseous media into a hollow space of the bipolar plate, or to the electrochemically active region.
Preferably, the conducting of media through the electrochemically active region is effected in a manner such that the location of the introduction of the medium and the location of the leading-out of the medium is effected at respective maximally distanced points of the
5 PCT/EP2008/008540 electrochemically active region. By way of this, the basic requirements for obtaining a distribution which is as plane as possible are created, and thereby a meandering leading is useful, even if dead-end layouts are possible. With such ones however, a flow resistance within the electrochemically active region is always to be overcome, so that the medium always seeks "short cuts" or bypasses. For this reason, the present invention with the limitation elements is particularly useful here.
Further advantageous embodiments of the present invention are specified in the remaining dependent claims.
The invention is now explained with the help of several figures. These show:
Fig. 1 a to 1 c the construction of a fuel cell stack, Fig. 2a and 2b plan views of differently designed bipolar plates, Fig. 3a and 3b cross sections through a bipolar plate arrangement according to the invention (Fig. 3a) and a bipolar plate arrangement according to the state of the art (Fig. 3b), Fig. 4 curves of the cathode-side volume flow against back-pressure, with and without limitation elements, Fig. 5 a plan view of a further embodiment of a bipolar plate with limitation elements, Fig. 6 a illustration of a centering according to B-B from Fig. 5, Fig. 7 flow resistance curves of electrochemical systems according to the invention, with different compressions.
Fig. 1 a to 1 c show the basic construction of an electrochemical system in the form of a fuel cell stack 1. This comprises a layering of several fuel cell arrangements 12 (see Fig. 1 b). The layering of these fuel cell arrangements 12 is held together by end plates which e.g. via clamping bolts as shown in Fig, 1 c, apply a compressive stress to the layering of the fuel cell arrangements.
The construction of a fuel cell arrangement 12 is explained in more detail hereinafter.
Further advantageous embodiments of the present invention are specified in the remaining dependent claims.
The invention is now explained with the help of several figures. These show:
Fig. 1 a to 1 c the construction of a fuel cell stack, Fig. 2a and 2b plan views of differently designed bipolar plates, Fig. 3a and 3b cross sections through a bipolar plate arrangement according to the invention (Fig. 3a) and a bipolar plate arrangement according to the state of the art (Fig. 3b), Fig. 4 curves of the cathode-side volume flow against back-pressure, with and without limitation elements, Fig. 5 a plan view of a further embodiment of a bipolar plate with limitation elements, Fig. 6 a illustration of a centering according to B-B from Fig. 5, Fig. 7 flow resistance curves of electrochemical systems according to the invention, with different compressions.
Fig. 1 a to 1 c show the basic construction of an electrochemical system in the form of a fuel cell stack 1. This comprises a layering of several fuel cell arrangements 12 (see Fig. 1 b). The layering of these fuel cell arrangements 12 is held together by end plates which e.g. via clamping bolts as shown in Fig, 1 c, apply a compressive stress to the layering of the fuel cell arrangements.
The construction of a fuel cell arrangement 12 is explained in more detail hereinafter.
6 PCT/EP2008/008540 Fig. I a shows the inner construction of a fuel cell arrangement 12 in the form of an exploded drawing. This is firstly a cell (for example a fuel cell) 2, which comprises a polymer membrane which is capable of conducting ions and which at least in an electrochemically active region 6 has a catalytic layer on both sides. Moreover, two bipolar plates 3 are provided in the fuel cell arrangement 12, between which the fuel cell 2 is arranged. Moreover, a gas diffusion layer 9 is arranged in the region between each bipolar plate and the adjacent fuel cell 2. A bead which is not shown and which is essentially peripheral in the edge region of the bipolar plates, forms a boundary wall and thus ensures the sealing of the electrochemically active region 6, so that no cooling fluid or media may exit to the outside from this region or vice versa.
Moreover, the bipolar plates 3 contain supply openings (interface channels) which are aligned to each other. On the one hand this is an opening 4 for leading through cooling fluid, wherein this opening is surrounded by a further bead arrangement. Moreover, an opening 5 for the supply and removal of media to the electrochemically active region is provided, which is limited by a further bead arrangement. Moreover, passage openings are provided for clamping bolts which are not shown in Fig. I a.
Fig. 2a shows a plan view of a section of a bipolar late according to the invention. Here, an opening for the supply and removal of media 5, which is surrounded by an annular-shaped full bead is shown. This full bead or bead arrangement comprises openings 5.1 for leading through fluid or gaseous media into a hollow space of the bipolar plate or towards the electrochemically active region. The shown bipolar plate 3 is of metal, wherein the channel structure 8 and the boundary wall 7 are designed as embossings unitary with the bipolar plate 3.
Here, only the upper left corner of the bipolar plate is shown in Fig. 2a for illustration.
The leading of media through the electrochemically active region 7 is however effected in a manner such that the location of the introduction of the medium and the location of the leading-out of the medium are positioned at points of the electrochemically active region maximally distanced to each other, preferably at the plane diagonals of the surface plane as it is shown in Fig. 2a.
The course of the boundary wall 7 is shown in a serpentine manner in Fig. 2a, at least in the section which is shown at the top on the right in Fig.2a.
Moreover, it is shown that with a serpentine course of the boundary wall 7, a portion of the boundary wall which lies closest to the channel structure 8, is connected via a limitation element 10 to the channel structure.
Moreover, the bipolar plates 3 contain supply openings (interface channels) which are aligned to each other. On the one hand this is an opening 4 for leading through cooling fluid, wherein this opening is surrounded by a further bead arrangement. Moreover, an opening 5 for the supply and removal of media to the electrochemically active region is provided, which is limited by a further bead arrangement. Moreover, passage openings are provided for clamping bolts which are not shown in Fig. I a.
Fig. 2a shows a plan view of a section of a bipolar late according to the invention. Here, an opening for the supply and removal of media 5, which is surrounded by an annular-shaped full bead is shown. This full bead or bead arrangement comprises openings 5.1 for leading through fluid or gaseous media into a hollow space of the bipolar plate or towards the electrochemically active region. The shown bipolar plate 3 is of metal, wherein the channel structure 8 and the boundary wall 7 are designed as embossings unitary with the bipolar plate 3.
Here, only the upper left corner of the bipolar plate is shown in Fig. 2a for illustration.
The leading of media through the electrochemically active region 7 is however effected in a manner such that the location of the introduction of the medium and the location of the leading-out of the medium are positioned at points of the electrochemically active region maximally distanced to each other, preferably at the plane diagonals of the surface plane as it is shown in Fig. 2a.
The course of the boundary wall 7 is shown in a serpentine manner in Fig. 2a, at least in the section which is shown at the top on the right in Fig.2a.
Moreover, it is shown that with a serpentine course of the boundary wall 7, a portion of the boundary wall which lies closest to the channel structure 8, is connected via a limitation element 10 to the channel structure.
7 PCT/EP2008/008540 Here, one may also deduce that the limitation element 10 runs essentially transversely to the boundary wall 7 or also essentially transversely to the elements of the channel structure 8 which are closest to the boundary wall (outermost) It may also be deduced from Fig. 2a that the limitation element 10 is designed as an extension of the channel structure 8, which merges into the boundary wall 7.
Fig. 2b shows an alternative embodiment of the bipolar plate shown in Fig. 2a.
In contrast to the bipolar plate shown in Fig. 2a, here however several limitation elements are provided. These are distanced to one another, so that two adjacent limitation elements 10 in each case form chambers between the channel structure 8 (thus the outermost elements of the channel structure) and the boundary wall 7.
The repetition distance of individual limitation elements hereby is preferably greater than 2 mm, particularly preferably greater than 5 - 10 mm.
It is therefore evident that limitation elements 10 are provided in the embodiments shown in Fig. 2a or Fig, 2b, which prevent a bypass (thus a shortcut) of medium between the boundary wall? as well as the outermost elements of the channel structure 8. This is designed in Fig. 2a as a single transverse web, in Fig. 2b as a multitude of transverse webs which then form corresponding chambers. It is important that these limitation elements 10 assume this function, thus are not designed as supply beads or inlets to cooling channels or media channels.
In this manner, the flow of medium which for example proceeds from the media supply opening 5 respectively 5.1, is forced through the channel structure 8 which is designed in a meandering manner, and this causes an increased backpressure which is thus also an indicator of greater reaction rates of media in the fuel cells.
Fig. 3a shows a cross-sectional view of a construction, which shows two bipolar plates 3 (for example according to Fig. 2a or Fig. 2b). Here, a fuel cell or a polymer electrolyte membrane (PEM) 2 is arranged between two bipolar plates 3. Moreover, a gas diffusion layer 9 is arranged on each side of the PEM 2, in the electrochemically active region.
This gas diffusion layer may be premanufactured and be designed as a direct integral component of a membrane electrode assembly, and the gas diffusion layers may also be provided as separate layers.
What is significant is that the height of the limitation elements 10 is selected in a manner such that the compression of the gas diffusion layer 9 in the contact region to the limitation
Fig. 2b shows an alternative embodiment of the bipolar plate shown in Fig. 2a.
In contrast to the bipolar plate shown in Fig. 2a, here however several limitation elements are provided. These are distanced to one another, so that two adjacent limitation elements 10 in each case form chambers between the channel structure 8 (thus the outermost elements of the channel structure) and the boundary wall 7.
The repetition distance of individual limitation elements hereby is preferably greater than 2 mm, particularly preferably greater than 5 - 10 mm.
It is therefore evident that limitation elements 10 are provided in the embodiments shown in Fig. 2a or Fig, 2b, which prevent a bypass (thus a shortcut) of medium between the boundary wall? as well as the outermost elements of the channel structure 8. This is designed in Fig. 2a as a single transverse web, in Fig. 2b as a multitude of transverse webs which then form corresponding chambers. It is important that these limitation elements 10 assume this function, thus are not designed as supply beads or inlets to cooling channels or media channels.
In this manner, the flow of medium which for example proceeds from the media supply opening 5 respectively 5.1, is forced through the channel structure 8 which is designed in a meandering manner, and this causes an increased backpressure which is thus also an indicator of greater reaction rates of media in the fuel cells.
Fig. 3a shows a cross-sectional view of a construction, which shows two bipolar plates 3 (for example according to Fig. 2a or Fig. 2b). Here, a fuel cell or a polymer electrolyte membrane (PEM) 2 is arranged between two bipolar plates 3. Moreover, a gas diffusion layer 9 is arranged on each side of the PEM 2, in the electrochemically active region.
This gas diffusion layer may be premanufactured and be designed as a direct integral component of a membrane electrode assembly, and the gas diffusion layers may also be provided as separate layers.
What is significant is that the height of the limitation elements 10 is selected in a manner such that the compression of the gas diffusion layer 9 in the contact region to the limitation
8 PCT/EP2008/008540 elements 10 is greater than in the contact region to the channel structure 8.
This is also indicated in an illustrated manner in Fig. 3a by the narrower hatching.
It is also to be seen that the boundary wall 7 has a greater height with respect to a base plane 11 of the bipolar plate 3 than the predominant elevation of the channel structure with respect to this base plane (this is indicated by the double arrows in Fig.
3a). It is likewise evident that the limitation elements 10, starting from this base plane 11 of the bipolar plate 3, have at least the height of the greatest elevation of the channel structure 8, however at the most the height of the boundary wall 7 with respect to the base plane (this also is evident by the double arrows in Fig. 3a).
In contrast to this, Fig. 3b shows an arrangement which has no limitation elements and with which an additional compression of the gas diffusion layer in the outer edge region is not given.
The figures which were referred to until now, in particular the Fig. la to lc, 2a, 2b as well as 3a, thus show a bipolar plate 3, wherein this comprises a base plane 11, and a channel structure 8 projecting from this base plane, as well as openings 5 for the supply and removal of media are provided, and the channel structure as well as the openings are surrounded by a boundary wall 7, and at least one limitation element 10 is provided in the region between the boundary wall and the outer edge of the channel structure, for preventing medium from bypassing in the border region between the boundary wall 7 and the channel structure 8.
Thus what is shown in the previously mentioned figures is also an electrochemical system 1 consisting of a layering of several cells 2 which in each case are separated from one another by bipolar plates 3, wherein the bipolar plates comprise openings for cooling 4 or the removal and supply 5 of operating media to the cells, and the layering may be set under mechanical compressive stress, wherein at least one cell comprises an electrochemically active region 6 which is surrounded by a boundary wall 7 of the bipolar plate, and a channel structure 8 of the bipolar plate is provided within the electrochemically active region for a uniform distribution of media, wherein at least one gas diffusion layer 9 is provided for the micro-distribution of medium, and limitation elements 10 are provided in the border region between the channel structure as well as the boundary wall, for avoiding the fluid bypassing between the channel structure and the boundary wall in the electrochemically active region (thus not the cooling region), and the gas diffusion layer covers the channel structure and/or at least parts of the limitation elements. Thus a clamping or a strong pressing of the gas diffusion layer in the edge region is achieved on account of this covering, and an even better sealing occurs on account of this, since not only the height of the boundary wall, but also the compression of the gas diffusion layer in this region ensures a prevention of the bypass (flowing-past/shortcut).
This is also indicated in an illustrated manner in Fig. 3a by the narrower hatching.
It is also to be seen that the boundary wall 7 has a greater height with respect to a base plane 11 of the bipolar plate 3 than the predominant elevation of the channel structure with respect to this base plane (this is indicated by the double arrows in Fig.
3a). It is likewise evident that the limitation elements 10, starting from this base plane 11 of the bipolar plate 3, have at least the height of the greatest elevation of the channel structure 8, however at the most the height of the boundary wall 7 with respect to the base plane (this also is evident by the double arrows in Fig. 3a).
In contrast to this, Fig. 3b shows an arrangement which has no limitation elements and with which an additional compression of the gas diffusion layer in the outer edge region is not given.
The figures which were referred to until now, in particular the Fig. la to lc, 2a, 2b as well as 3a, thus show a bipolar plate 3, wherein this comprises a base plane 11, and a channel structure 8 projecting from this base plane, as well as openings 5 for the supply and removal of media are provided, and the channel structure as well as the openings are surrounded by a boundary wall 7, and at least one limitation element 10 is provided in the region between the boundary wall and the outer edge of the channel structure, for preventing medium from bypassing in the border region between the boundary wall 7 and the channel structure 8.
Thus what is shown in the previously mentioned figures is also an electrochemical system 1 consisting of a layering of several cells 2 which in each case are separated from one another by bipolar plates 3, wherein the bipolar plates comprise openings for cooling 4 or the removal and supply 5 of operating media to the cells, and the layering may be set under mechanical compressive stress, wherein at least one cell comprises an electrochemically active region 6 which is surrounded by a boundary wall 7 of the bipolar plate, and a channel structure 8 of the bipolar plate is provided within the electrochemically active region for a uniform distribution of media, wherein at least one gas diffusion layer 9 is provided for the micro-distribution of medium, and limitation elements 10 are provided in the border region between the channel structure as well as the boundary wall, for avoiding the fluid bypassing between the channel structure and the boundary wall in the electrochemically active region (thus not the cooling region), and the gas diffusion layer covers the channel structure and/or at least parts of the limitation elements. Thus a clamping or a strong pressing of the gas diffusion layer in the edge region is achieved on account of this covering, and an even better sealing occurs on account of this, since not only the height of the boundary wall, but also the compression of the gas diffusion layer in this region ensures a prevention of the bypass (flowing-past/shortcut).
9 PCT/EP2008/008540 Fig. 4 shows the diagram of a volume flow in litres per minute against the back-pressure in millibars, for an electrochemical system.
The left graph shows a conventional design on the cathode side (for example with a cross section according to Fig. 3b), with which a flow of medium bypassing the gas diffusion layer is possible. The right graph shows a compression of the gas diffusion layer with limitation elements, so that a bypass is prevented or limited by way of this. It is shown here that with the same volume flow, a much greater back-pressure is present. This is an indication that the medium does not simply pass without being led through the electrochemically active field. By way of this a constant reaction is forced since the reaction medium no longer bypasses (flows past) in a non-used manner.
Fig. 5 shows a further embodiment of a bipolar plate according to the invention. Here, channel structures 8 are provided in the electrochemically active region 6 which is surrounded by a boundary wall, which are mainly designed as disjunct, thus individual raised elements. Here, it is again the case of a bipolar plate with a flowfield (electrochemically active region), with which the reaction medium is led from the top left in a diagonal manner to the bottom right (exit 5 there). Limitation elements 10 are provided at two locations (bottom left and top right), which prevent an undesired bypass.
Fig. 6 shows a cross section through B-B of the plate arrangement of Fig. 5 in an enlarged scale. Here, it is to be seen that there a bipolar plate is constructed of two plates, wherein the at least one limitation element 10 is hollow on the side which is distant to the electrochemically active side, and this hollow space is provided as a complementary space for inserting the second plate of the bipolar plate. In this manner, an additional centering of both plates is carried out, so that the dimensional accuracy of the complete bipolar plate is increased by way of this.
Fig. 7 shows (similarly as it has been shown already above in Fig. 4) the volume flow of (dry) air in litres per minute, against the back-pressure (in millibar). Here, one may also see that with increasing compression values (compressive stress) in the complete assembly (see Fig. I c) and with an equal volume flow of air, a significantly increased back-pressure arises and that in this manner uniformly reproducible values can be set.
The left graph shows a conventional design on the cathode side (for example with a cross section according to Fig. 3b), with which a flow of medium bypassing the gas diffusion layer is possible. The right graph shows a compression of the gas diffusion layer with limitation elements, so that a bypass is prevented or limited by way of this. It is shown here that with the same volume flow, a much greater back-pressure is present. This is an indication that the medium does not simply pass without being led through the electrochemically active field. By way of this a constant reaction is forced since the reaction medium no longer bypasses (flows past) in a non-used manner.
Fig. 5 shows a further embodiment of a bipolar plate according to the invention. Here, channel structures 8 are provided in the electrochemically active region 6 which is surrounded by a boundary wall, which are mainly designed as disjunct, thus individual raised elements. Here, it is again the case of a bipolar plate with a flowfield (electrochemically active region), with which the reaction medium is led from the top left in a diagonal manner to the bottom right (exit 5 there). Limitation elements 10 are provided at two locations (bottom left and top right), which prevent an undesired bypass.
Fig. 6 shows a cross section through B-B of the plate arrangement of Fig. 5 in an enlarged scale. Here, it is to be seen that there a bipolar plate is constructed of two plates, wherein the at least one limitation element 10 is hollow on the side which is distant to the electrochemically active side, and this hollow space is provided as a complementary space for inserting the second plate of the bipolar plate. In this manner, an additional centering of both plates is carried out, so that the dimensional accuracy of the complete bipolar plate is increased by way of this.
Fig. 7 shows (similarly as it has been shown already above in Fig. 4) the volume flow of (dry) air in litres per minute, against the back-pressure (in millibar). Here, one may also see that with increasing compression values (compressive stress) in the complete assembly (see Fig. I c) and with an equal volume flow of air, a significantly increased back-pressure arises and that in this manner uniformly reproducible values can be set.
Claims (20)
1. An electrochemical system (1), consisting of a layering of several cells (2), which in each case are separated from one another by way of bipolar plates (3), wherein the bipolar plates comprise openings for the cooling (4) or for the removal and supply of operating media (5) to the cells, and the layering may be set under mechanical compressive stress, wherein at least one cell comprises an electrochemically active region (6) which is surrounded by a boundary wall (7) of the bipolar plate, and a channel structure (8) of the bipolar plate is provided within the electrochemically active region, for the uniform media distribution, wherein at least one gas diffusion layer (9) is provided for the micro-distribution of media, characterised in that limitation elements (10) are provided in the border region between the channel structure as well as the boundary wall, for avoiding fluid from bypassing between the channel structure and the boundary wall, and the gas diffusion layer covers the channel structure and/or at least parts of the limitation elements.
2. A system according to claim 1, characterised in that the height of the limitation elements (10) is selected in a manner such that the compression of the gas diffusion layer (9) is greater in the contact region to the limitation elements (10) than in the contact region to the channel structure (8).
3. A system according to one of the preceding claims, characterised in that the limitation elements (10) are designed as extensions of the channel structure, which merge into the boundary walls.
4. A system according to one of the preceding claims, characterised in that one or more limitation elements (10) are provided.
5. A system according to claim 4, characterised in that single limitation elements are distanced to one another, so that two adjacent limitation elements (10) in each case form chambers between the channel structure and the boundary wall (7).
6. A system according to one of the claims 4 or 5, characterised in that the repetition distance of single limitation elements (10) is greater than 2 mm, preferably greater than 5 to 10 mm.
7. A system according to one of the preceding claims, characterised in that the boundary wall (7) runs in a serpentine manner.
8. A system according to claim 7, characterised in that with a serpentine course of the boundary wall (7), in each case the portion of the boundary wall, which lies closest to the channel structure (8) is connected to the channel structure via a limitation element (10).
9. A system according to one of the preceding claims, characterised in that the limitation elements (10) run essentially transversely to the boundary wall.
10. A system according to one of the preceding claims, characterised in that the limitation elements (10) run essentially transversely to the outermost elements of the channel structure (8).
11. A system according to one of the preceding claims, characterised in that with the design of the channel structures (8) as individual elements, the limitation elements (10) are present in a linear manner or likewise in the form of individual elements.
12. A system according to one of the preceding claims, characterised in that the boundary wall (7) with respect to a base plane (11) of the bipolar plate (3) has a greater height than the highest elevation of the channel structure in the adjacent vicinity of the boundary wall with respect to this base plane.
13. A system according to one of the preceding claims, characterised in that the limitation elements, proceeding from a base plane (11) of the bipolar plate, have at least the height of the predominant elevation of the channel structure (8).
14. A system according to one of the preceding claims, characterised in that the limitation elements (10) are designed as embossings in a bipolar plate (3).
15. A system according to one of the preceding claims, characterised in that a bipolar plate (3) is constructed of two plates, wherein the at least one limitation element (10) is hollow on the side which is distant to the electrochemically active side, and this hollow space is designed as a complementary space for inserting the second plate of the bipolar plate.
16. A system according to one of the preceding claims, characterised in that the boundary wall (7) has the shape of a bead, in particular a full bead or a half bead.
17. A system according to one of the preceding claims, characterised in that the bipolar plate (3) consists of metal.
18. A system according to one of the preceding claims, characterised in that the openings of the bipolar plate, for cooling (4) or for the removal or supply (5) of media, are provided with elastic bead arrangements, wherein these bead arrangements comprise openings for leading through fluid medium or gaseous medium into a hollow space of the bipolar plate, or to the electrochemically active region.
19. A system according to one of the preceding claims, characterised in that the leading of media through the electrochemically active region (6) is effected in a manner such that the location of the introduction of the medium and the location of the leading-out of the medium is effected at in each case maximally distanced points of the electrochemically active region.
20. A bipolar plate for use in an electrochemical system according to one of the preceding claims, characterised in that this has a base plane (11) and a channel structure (8) projecting from this base plane is provided, as well as openings for the supply and removal of media, and the channel structure as well as the openings are surrounded by a boundary wall (7) and that at least one limitation element (10) is provided in the region between the boundary wall and the outer edge of the channel structure, for preventing the medium from bypassing in the border region between the boundary wall (7) and the channel structure.
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PCT/EP2008/008540 WO2009043600A1 (en) | 2007-10-02 | 2008-10-02 | Electrochemical system |
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JP5239091B2 (en) | 2013-07-17 |
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WO2009043600A1 (en) | 2009-04-09 |
CA2701366C (en) | 2015-12-01 |
DE102007048184B3 (en) | 2009-01-22 |
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