WO2005106078A1

WO2005106078A1 - Electrochemical cells having current-carrying structures underlying electrochemical reaction layers

Info

Publication number: WO2005106078A1
Application number: PCT/CA2005/000669
Authority: WO
Inventors: Gerard Francis Mclean; Anna Stukas; Jeremy Schrooten
Original assignee: Angstrom Power Incorporated
Priority date: 2004-05-04
Filing date: 2005-05-03
Publication date: 2005-11-10
Also published as: US7632587B2; CN102208664B; US8232025B2; US20100183955A1; US20150072263A1; US20050250004A1; CA2564843C; CN1965108A; CA2564843A1; EP2431497A3; US8628890B2; US20120270132A1; CN102208664A; US9017892B2; EP1745162A4; EP2431497A2; HK1102014A1; CN1965108B; EP1745162A1; JP5271537B2

Abstract

An electrochemical cell structure has an electrical current-carrying structure which, at least in part, underlies an electrochemical reaction layer. The cell comprises an ion exchange membrane with a catalyst layer on each side thereof. The ion exchange membrane may comprise, for example, a proton exchange membrane. Some embodiments of the invention provide electrochemical cell layers which have a plurality of individual unit cells formed on a sheet of ion exchange membrane material.

Description

ELECTROCHEMICAL CELLS HAVING CURRENT-CARRYING STRUCTURES UNDERLYING ELECTROCHEMICALREACTIONLAYERS

Reference to Related Application .

[0001] This application claims priority from United States Patent Application

Nos. 60/567648 filed 4 May 2004, 60/608879 filed 13 September 2004, and

11/047560 filed 2 February 2005, all of which are hereby incorporated by reference herein.

Technical Field

[0002] The invention relates to electrochemical cells. The invention may be embodied in fuel cells, electrolysis cells and electrochemical cells of other types.

Background

[0003] A conventional electrochemical cell 10 is shown in Figure 1. Cell 10 may, for example, comprise a PEM (proton exchange membrane) fuel cell. Cell 10 has a manifold 12 into, which is introduced a fuel, such as hydrogen gas. The fuel can pass through a porous current-carrying layer 13A into an anode catalyst layer 14A, where the fuel undergoes a chemical reaction to produce free electrons and positively charged ions (typically protons). The free electrons are collected by current-carrying layer 13A, and the ions pass through an electrically-insulating ion exchange membrane 15. Ion exchange membrane 15 lies between anode catalyst layer 14A and a cathode catalyst layer 14B. Cell 10 has a manifold 16 carrying an oxidant (e.g. air or oxygen). The oxidant can pass through a porous current-carrying layer 13B to access cathode catalyst layer 14B.

[0004] As shown in Figure 1A, electrons travel from the sites of chemical reactions in anode catalyst layer 14A to current-carrying layer 13A. Protons (or other positively charged ions) travel into and through ion exchange membrane 15 in a direction opposite to the direction of electron flow. Electrons collected in current- carrying layer 13A travel through an external circuit 18 to the porous current-carrying layer 13B on the ca, »de side of cell 10. In such cells, electron flow and ion flow occur in generally opposite directions and are both substantially perpendicular to the plane of ion exchange membrane 15.

[0005] Catalyst layers 14A and 14B must be "dual species conductive" (i.e. they must provide conductive paths for the flow of both electrons and ions). Ion exchange membrane 15 must be single species conductive (i.e. it must permit ions to flow while providing electrical insulation to avoid internal short-circuiting of cell 10).

[0006] Many electrochemical devices include some form of porous conductive reactant diffusion media to carry current away from a catalyst layer. This compromises the ability to transport reactants to the catalyst sites, and introduces a difficult material challenge. Further, there are manufacturing and cost issues associated with the inclusion of reactant diffusion layers. A major problem in designing high performance electrochemical cells is to provide current-carrying layers which permit current to be passed into or withdrawn from the cell while permitting reactants to enter the cell and products of the reactions to be removed from the cell.

[0007] Despite the vast amount of fuel cell research and development that has been done over the past decades there remains a need for more efficient electrochemical cells that can be produced cost effectively and which provide improved access for reactants to the electrochemical reaction sites.

Summary of the Invention ^'

[0008] The invention relates to electrochemical cells such as fuel cells or electrolyzers. Some embodiments of the invention have application in electrochemical cells of other types such as those used for chlor-alkali processing. Some embodiments of the invention provide electrochemical cell layers comprising arrays of individual or "unit" cells.

[0009] One aspect of the invention provides a thin layer cell structure comprising an ion exchange membrane having an electrochemical reaction layer on each side thereof. The ion exchange membrane may comprise a layer of unitary construction, or may comprise a composite layer made up of more than one material. The ion exchange membrane may comprise, for example, a proton exchange membrane. An electrical current-carrying structure at least in part underlies one of the electrochemical reaction layers.

[0010] Another aspect of the invention provides core assemblies for electrochemical cells. A core assembly comprises an ion exchange membrane; an electrically conducting electrochemical reaction layer on at least a first side of the ion exchange membrane; and, an electrically-conductive current-carrying structure in electrical contact with the electrochemical reaction layer. An outer surface of the electrochemical reaction layer overlies at least a portion of the current-carrying structure.

[0011] A further aspect of the invention provides methods for operating an electrochemical cell. Such methods comprise providing an electrochemical cell having: a catalyst-containing electrochemical reaction layer having an outer face and an inner face; an electrical current-carrying structure underlying the electrochemical reaction layer at least in part; and an ion-conducting layer in contact with the inner face of the electrochemical reaction layer; allowing a reactant to diffuse into the electrochemical reaction layer; allowing the reactant to undergo a catalysed electrochemical reaction to produce an ion at a location in the electrochemical reaction layer between a surface of the electrochemical layer and the current-carrying layer; and, allowing the ion to travel to the ion-conducting layer along a path that avoids the current-carrying structure.

[0012] Further aspects of the invention and features of specific embodiments of the invention are described below.

Brief Description of the Drawings

[0013] In drawings which illustrate non-limiting embodiments of the invention: Figure 1 is a cross-sectional schematic diagram of a prior art electrochemical cell; Figure 1 A is an enlarged schematic view of a portion of the cell of Figure 1; Figures 2A-D are schematic views of unit cell structures according to embodiments of the invention; Figure 3 is a schematic diagram of an electrode according to an embodiment of the invention; Figure 4 is a schematic diagram showing electron and proton conduction paths according to an embodiment of the invention; Figure 5 is a schematic view of a unit cell structure according to another embodiment of the invention; Figure 6 is a cross section through a membrane electrode assembly of an alternative embodiment of the invention wherein unit cells are connected in series; Figure 6A is a schematic illustration showing current flow and proton flow in the membrane electrode assembly of Figure 6; Figure 6B is a cross section through a membrane electrode assembly in which unit cells are interconnected by current conductors embedded in a substrate; Figure 7 is a partial plan view of an electrochemical cell layer having an array of hexagonal unit cells; Figures 8A, 8B and 8C are respectively schematic views showing electrochemical cell layers having a plurality of unit cells connected in parallel, in series and in series-parallel; Figure 9 is a side view of a pleated structure on which unit cells according to the invention may be disposed; Figure 10 is an exploded view of a fuel cell device according to an embodiment of the invention; Figure 10A shows the fuel cell device of Figure 10 in assembled form; Figure 11 shows a fuel cell device according to another embodiment of the invention; Figure 12 shows a stack of fuel cell layers according to another embodiment of the invention; and Figure 13 is a section through a fuel cell having a filter layer overlying a catalyst layer.

Description

[0014] Throughout the following description, specific details are set forth in order to provide a more thorough understanding of the invention. However, the invention may be practised without these particulars. In other instances, well known elements have not been shown or described in detail to avoid unnecessarily obscuring the invention. Accordingly, the specification and drawings are to be regarded in an illustrative, rather than a restrictive, sense.

[0015] The invention relates to electrochemical cells such as fuel cells or electrolyzers, and may also have application in other types of electrochemical cells, such as those used for chlor-alkali processing. Some embodiments of the invention provide electrochemical cell layers comprising arrays of individual or "unit" cells. [0016] Electrochemical cells according to some embodiments of the invention have a thin layer cell structure wherein an electrical current-carrying structure at least in part underlies an electrochemical reaction layer (referred to herein as a "catalyst layer"). Each cell comprises an ion exchange membrane having a catalyst layer on each side thereof. The ion exchange membrane may comprise, for example, a proton exchange membrane. Certain embodiments of the invention permit construction of an electrochemical cell layer comprising a plurality of individual unit cells formed on a sheet of ion exchange membrane material.

[0017] The ion exchange membrane may comprise a layer of unitary construction, or may comprise a composite layer made up of more than one material. Some examples of composite structures are described in the commonly-owned United States patent application entitled "MICRO-STRUCTURED MEMBRANES AND ELECTROCHEMICAL CELLS INCORPORATING SUCH MEMBRANES" filed concurrently herewith, which is hereby incorporated by reference herein.

[0018] The configuration of the current-carrying structures in preferred embodiments of the invention provides reactants with improved access to the catalyst layer, and permits the construction of electrochemical cells which are thinner than similar prior art electrochemical cells of the type having current-carrying layers positioned on outer surfaces of the catalyst layers. Throughout this description, the terms "outer" and "inner" are respectively used to refer to directions closer to and farther from the center of the ion exchange membrane.

[0019] Figures 2A and 2B show unit cell structures 20A and 20B according to alternative embodiments of the invention. Structures 20 A and 20B are similar to one another, and each comprise current-carrying structures 23A and 23B positioned on opposite sides of an ion exchange membrane 25. Electrochemical reaction layers 24 A and 24B are positioned on the outside of current-carrying structures 23A and 23B and ion exchange membrane 25. The difference between structures 20A and 20B is that in structure 20A current-carrying structures 23A and 23B are positioned on the outer surfaces of ion exchange membrane 25, while in structure 20B current-carrying structures 23A and 23B are embedded in the outer surfaces of ion exchange membrane 25.

[0020] Figures 2C and 2D show unit cell structures 20C and 20D according to further alternative embodiments of the invention. In structure 20C, current-carrying structures 23A and 23B are formed on a substrate 30. Substrate 30 is constructed from a non-conducting material.

[0021] Substrate 30 is penetrated by an opening 32. Opening 32 is filled with an ion-conducting material. The ion-conducting material may comprise an ionomer or electrolyte suitable to the application. The ion-conducting material may extend outward to the outer edges of current-carrying structures 23 A and 23B to form ion exchange membrane 25 of unit cell structure 20C. In the illustrated embodiment, opening 32 is round, but this is not necessary. Opening 32 may be of any suitable shape. In some embodiments, opening 32 is long and narrow. In some embodiments, each unit cell has a plurality of openings 32.

[0022] In some embodiments, openings 32 comprise a pattern of openings, which may be microstructured openings, as described, for example in the commonly- assigned application entitled "MICRO-STRUCTURED MEMBRANES AND ELECTROCHEMICAL CELLS INCORPORATING SUCH MEMBRANES" which is referred to above.

[0023] Examples of materials that may be suitable for substrate 30 in specific applications include:

• printed circuit board (PCB) material, polyamide films; polyimide films such as Kapton™, polyethylene films, Teflon™ films, other polymer films, reinforced composite materials such as fibreglass, suitable non-polymer materials such as silicon or glass. In some applications it is advantageous that substrate 30 be flexible. In such applications it is desirable that substrate 30 be made of a flexible material.

[0024] In structure 20D, current-carrying structures 23A and 23B are formed on proton conducting membrane 25 and there is no substrate 30. Structure 20D differs from structure 20 A in that current-carrying structures 23 A and 23B project respectively through the outer surfaces of catalyst layers 24A and 24B. A structure like structure 20D may have its catalyst layers 24A and 24B divided into isolated areas by current-carrying structures 23 A and 23B. Structure 20D has the disadvantage that the exposed surface area of catalyst areas 24A and 24B is somewhat reduced in comparison to structures 20A, 20B, and 20C.

[0025] In each of unit cell structures 20A-D, current-carrying structures 23A and 23B underlie portions of catalyst layers 24A and 24B respectively. In the embodiments of Figures 2A-C, ions liberated at reaction sites which are over current- carrying structures 23A (or, in Figure 2C, over substrate 30) are blocked from flowing directly into and through ion exchange membrane 25 by the shortest straight-line path. Ions liberated at such sites must take longer paths to reach catalyst layer 24B.

However, by appropriately positioning current-carrying structures 23A and 23B, the thicknesses of the various layers and other dimensions (such as the width D of opening 32 in Figure 2C) one can achieve a situation in which the lengths of paths taken by ions and electrons are not very much longer than corresponding path lengths in comparable prior art electrolytic cells.

[0026] The embodiment of Figure 2C trades off increased path length for proton conduction against the increased mechanical ruggedness resulting from the presence of substrate 30.

[0027] A feature of structures 20A through 20C is that the current-carrying structures 23A and 23B are not required to be porous because it is not necessary for reactants to pass through these structures.

[0028] Adjacent unit fuel cells may be connected in parallel by either providing current-carrying structures 23 A and 23B that are common to the adjacent unit cells, or by electrically interconnecting current-carrying structures 23 A of adjacent cells and current-carrying structures 23B of adjacent cells. Adjacent unit cells may also be electrically isolated from one another, in which case they may be connected in series, as discussed below with reference to Figures 6 and 6B. Electrical isolation of unit cell structures may be provided by rendering portions of a catalyst layer non-conducting electrically, by making a catalyst layer discontinuous in its portions between unit cells and/or by providing electrically insulating barriers between the unit cell structures.

[0029] Optimising catalyst layer 24A to promote reactions does not always result in the highest electrical conductivity in catalyst layer 24A. The materials used in the catalyst layer may not be extremely good electrical conductors. However, the losses resulting from the electrical resistivity of catalyst layer 24A can be minimized by laying out each unit cell so that the distance between any point in catalyst layer 24A and the closest part of current-carrying member 23A is small. [0030] For example, in some embodiments of the invention the longest path length from any point within either catalyst layer 24A, 24B to the corresponding current-carrying member 23 A, 23B is 5 mm. In other embodiments, the longest path length from any point within either catalyst layer 24A, 24B to the corresponding current-carrying member 23 A, 23B is 0.5 mm. Even smaller diameters are also possible. In general, reducing the diameter decreases the ohmic losses associated with electrical current conduction in the catalyst layer. However, as the structure becomes smaller, the volume taken up current carrying members 23A, 23B increases in proportion to the volume of the overall structure, and the space-efficiency of the structure can suffer.

[0031] Figure 3 illustrates a geometry that may be used for approximating the potential drop of an electrode 34 (which may be either an anode or a cathode). Electrode 34 comprises a current-carrying structure 23A having a skin of ion exchange material 25A therein and catalyst layer 24A disposed outside thereof. Only the portion of catalyst layer 24A which is above current-carrying structure 23A is depicted in Figure 3. Electrode 34 is positioned opposite a corresponding electrode (not shown in Figure 3) on an outer surface of an ion exchange membrane (not shown in Figure 3) which may or may not be a composite membrane having substrate 30 embedded therein. In the Figure 3 embodiment, current-carrying structure 23A comprises an annular trace, wherein D_τ is the outer diameter of the circular trace, T_CL and T_τ are the thicknesses of catalyst layer 24A and the circular trace, respectively, and W_τ is the width of the circular trace. In some embodiments, the ratio of trace diameter to trace width (Dj/W_τ) is at least 10.

[0032] Current-carrying structures 23A and 23B are constructed from electrically conductive materials. The following table lists some suitable materials for current-carrying structures 23 A and 23B and their electrical conductivities:

[0033] Any electrically conductive materials may be used to construct current- carrying structures 23 A and 23B. In some embodiments, current-carrying structures 23A and 23B are constructed from metals that are either noble to begin with or are coated with a suitable material (Such as PEMCoat™ from INEOS Chlor™ Americas Inc., Wilmington, Delaware) so that they resist corrosion. Corrosion can be a problem when metallic conductors are used in electrochemical cells, and fuel cells in particular. The cross sectional dimensions of current-carrying structures 23A and 23B can be chosen based on the total current desired to be carried and the electrical losses which are deemed acceptable in the design.

[0034] Current-carrying structures 23A and 23B may have thicknesses, for example, in the range of 5-75 μm. In some embodiments, the thickness of current- carrying structures 23A and 23B is in the range of 25-50 μm. Current-carrying structures 23 A and 23B need not have the same thickness. Where current-carrying structures 23A and 23B comprise annular traces, the traces may have a width of 5-200 μm. In some embodiments, the traces may have a thickness on the order to 5 μm and a width on the order of 25 μm. Current-carrying structures 23A and 23B can be formed using any suitable techniques. For example, various printed circuit board fabrication techniques may be used to form structures 23A and 23B. Laminating, PVD, sputtering and plating are examples of techniques that may be used alone or in combination to make the traces.

[0035] Catalyst layers 24A and 24B may be constructed from materials which conduct both electrons and the ions formed in the reactions which occur in the cell in which they are employed. (The ions are protons in hydrogen-fuelled PEM fuel cells). Catalyst layers 24A and 24B may comprise any type of electrocatalyst suitable for the application at hand. Catalyst layers 24A and 24B may comprise electrically- conductive porous sintered powder materials, for example. For fuel cells the catalyst layers may comprise platinum on carbon, for example. In some embodiments, catalyst layers 24A and/or 24B comprise mixtures of carbon black and one or more of PTFE powder, PVDF powder, such as Kynar™ powder, and silicon oxide powder. The carbon black may comprise any suitable finely divided carbon material such as one or more of acetylene black carbon, carbon fibers, carbon needles, carbon nanotubes, carbon nanoparticles .

[0036] In some embodiments, catalyst layers 24A and 24B are formed of materials having electrical conductivities in the range of 50-200 S/m. Each catalyst layer 24A, 24B may be made up of several layers of different compositions.

[0037] In some embodiments, catalyst layers 24A and 24B have thicknesses of

250 μm or less. In some embodiments, the thickness of catalyst layers 24A and 24B is about 10-25 μm. The thickness of catalys layers 24A and 24B may be about 20 μm, for example. Catalyst layers 24A and 24B need not have the same thickness.

[0038] Where ion exchange membrane 25 has a composite structure such as a structure including a substrate 30, substrate 30 provides mechanical strength to membrane 25. The presence of substrate 30 permits membrane 25 to be made thinner than ordinary proton conducting membranes. This decreased thickness can compensate to at least some degree for the more tortuous paths taken by protons which are liberated at locations which are not immediately adjacent to apertures in substrate 30. In some embodiments, the thickness of membrane 25 is in the range of about 5 μm to about 250 μm. The thickness of membrane 25 may be about 25 μm, for example.

[0039] Figure 4 shows a portion of a unit cell structure 20E according to another embodiment of the invention. Unit cell structure 20E constitutes a PEM fuel cell with substrate 30 having a plurality of openings 32. A proton exchange material fills openings 32 and surrounds substrate 30 to form ion exchange membrane 25. Figure 4 shows paths taken by protons (H⁺) from three example reaction sites 33 A,

33B and 33C in catalyst layer 24A of structure 20E, through ion exchange membrane 25 and into catalyst layer 24B to three other example reaction sites 33D, 33E and 33F. Figure 4 also shows the paths taken by electrons (e^~) from reaction sites 33A, 33B and 33C to current-carrying structure 23A, and from current-carrying structure 23B to reaction sites 33D, 33E and 33F.

[0040] It can be seen that from reaction site 33A and 33B the electron and proton paths through catalyst layer 24A are roughly equal in length. From reaction site 33A, which is over current-carrying structure 23A, the path taken by electrons through catalyst layer 24A is shorter than that taken by protons which must detour around current-carrying structure 23A. From reaction site 33C the path taken through catalyst layer 24 A by protons is significantly shorter than that taken by electrons. In the illustrated examples, the paths taken by electrons and protons in catalyst layer 24B to reach reaction sites 33D, 33E and 33F have lengths similar to the lengths of the paths taken in catalyst layer 24A.

[0041] The paths taken by protons through ion exchange membrane 25 is not equal, due to the presence of substrate 30. The protons must detour through openings 32. In the examples illustrated, the path taken by the proton travelling from reaction site 33B to reaction site 33E has the shortest distance through ion exchange membrane 25, while the path taken by the proton travelling from reaction site 33C to reaction site 33F has the longest distance through ion exchange membrane 25.

[0042] It can be seen in Figure 4 that the conductive species generated in catalyst layer 24A (protons and electrons) both flow in generally the same direction (e.g. downward in Figure 4) to get from the reaction site where they are liberated to the conductor that will carry them. Likewise, the conductive species used in the reactions in catalyst layer 24B both flow in generally the same direction (e.g. downward in Figure 4) to get from the conductor to the reaction site.

[0043] Figure 5 shows an electrochemical cell layer 36 comprising two unit cell structures 20F. In the Figure 5 embodiment, cell layer 36 is formed from a nonconducting sheet 26 which has been treated to form two ion-conducting regions 27. Sheet 26 may, for example, be constructed of a copolymer of tetrafluoroethylene and perfluoro-3, 6-dioxa-4-methyl-7-octenesulfonyl fluoride (which is a resin precursor to Nafion™), and may be selectively treated by a hydrolyzation process to form ion-conducting regions 27, as described, for example in the commonly-assigned application entitled "MICRO-STRUCTURED MEMBRANES AND ELECTROCHEMICAL CELLS INCORPORATING SUCH MEMBRANES" which is referred to above.

[0044] Current-carrying structures 23A and 23B are placed on opposite sides of sheet 26 around the periphery of each ion-conducting region 27. Current-carrying structures 23A and 23B may be ring-shaped, or may have different shapes. Ion- conducting skins 25A and 25B may optionally be placed on the outer surfaces of each ion-conducting region 27 within current-carrying structures 23A and 23B, respectively. Ion-conducting skins 25A and 25B and ion-conducting region 27 together form ion-conducting membrane 25 for each structure 20F. Catalyst layers 24A and 24B are formed on the outer surfaces of current-carrying structures 23A and 23B and ion-conducting skins 25A and 25B for each of cell structures 20F. In the illustrated embodiment, catalyst layers 24A and 24B for each cell structure 20F are formed separately. However, a single catalyst layer 24A could cover one side of both structures 20F, and another single catalyst layer 24B could cover the other side of both structures 20F, if cell structures 20F are to be connected in parallel.

[0045] Neighboring unit cells may be electrically isolated from one another. In this case it is possible to electrically interconnect the unit cells in arrangements other than parallel arrangements. Vias may be used to interconnect adjacent unit cells in series. In embodiments in which unit cells are connected in series, catalyst layers 24A of the series connected cells are electrically isolated from one another. Figure 6 shows a cross section through a part of an electrochemical cell layer 40 in which a number of unit cells 42 are connected in series. Figure 6 A illustrates schematically the paths taken by protons and electrons in the assembly of Figure 6.

[0046] In the embodiment of Figure 6, regions 44 are electrically insulating.

Regions 44 may comprise a dielectric material, an air gap, or the like. Regions 44 electrically isolate adjoining electrochemical unit cells from one another.

[0047] Current-carrying structure 23A of each unit cell 42 is connected to the current-carrying structure 23B of the adjacent unit cell 42 by an electrically conductive pathway 23C which passes through a via in substrate 30.

[0048] Figure 6B shows an electrochemical cell layer 40A wherein unit cells are interconnected with one another by way of electrically conducting paths 46 embedded in substrate 30. Conducting paths 46 may be connected to current-carrying structures 23A and/or 23B by way of electrically conducting vias 47 formed in substrate 30. The conducting paths may be used to interconnect unit cells in series and/or in parallel with one another. A number of independent sets of conducting paths 46 may be provided in or on substrate 30.

[0049] Electrochemical cell layer 40A of Figure 6B may be constructed using a multi-layer circuit board such as a flex circuit. This provides increased current- carrying capacity for the overall current collection system without reducing the surface area available for the cell reactions in the catalyst layers 24A and 24B.

[0050] Unit cells according to embodiments of the invention may have any suitable shapes and may be arrayed in any suitable manner. Figure 7 shows one example of an electrochemical cell layer comprising a plurality of unit cell structures 20D wherein the unit cells have a hexagonal configuration. The entire surface of structures 20D could be covered with a catalyst layer 24A if desired. In alternative embodiments the unit cells have elongated shapes in which a dimension along a principle axis is significantly longer than a transverse dimension. For example, such unit cells may be shaped like elongated ellipses, elongated rectangles, elongated obround shapes or the like. The longer dimension of such unit cells may, for example, be at least 2, 5 or 10 times larger than the transverse shorter dimension.

[0051] It can be appreciated that various embodiments of the invention described above (e.g., structures 20D and 40 or 40A) can be combined to provide assemblies of unit cells which are electrically interconnected in a series-parallel arrangement of any desired complexity. Generally available electrical conductors (such as suitable metals) have much less resistance to the flow of electrons than do generally available proton conductors to the flow of protons. Therefore, the conductors which carry electrons can have significantly smaller cross sectional areas than do the pathways which carry protons. Substrate 30 may comprise a multi-layer structure (as, for example, a multi-layer circuit board) in which case, conductors for carrying electrical currents may be embedded inside substrate 30. [0052] Figures 8A, 8B and 8C show various possible ways in which the unit cells in a small array (in this example, a very small array having only 16 unit cells) may be interconnected. In Figure 8A, unit cells 42 are connected in parallel. The output voltage is 1 (where 1 is the output voltage of a single unit cell) and the output current is -V(in this case 16 times the maximum current of one unit cell). An open circuit failure of any one or more unit cells 42 will not prevent the array from operating (at a reduced output current) at the rated voltage (1 unit). However, a short- circuit failure of any one unit cell can prevent the entire array from functioning.

[0053] In Figure 8B, unit cells 42 are arranged in a series configuration. The voltage output is N (in this case 16 times the voltage of a single unit cell). The maximum current output is 1. An open circuit failure of any one or more unit cells will prevent the array from operating. A short-circuit failure of any one or more unit cells will not prevent the array from providing current at a (reduced) maximum output voltage.

[0054] Figure 8C shows a number of unit cells 42 arranged in a series-parallel configuration. In this case, the array is interconnected so that there are four groups of unit cells connected in series. Each group of unit cells comprises four unit cells connected in parallel. Note that each unit cell is connected to a neighbor which is diagonally adjacent. Note that one of the groups of parallel connected unit cells is split into two parts which are located in spatially separated areas of the array. In some embodiments of the invention, unit cells of a group of unit cells are spatially distributed. This makes it less likely that a failure caused by trauma to an area of the array will cause all of the unit cells of a group to fail.

[0055] In the embodiment of Figure 8C the output voltage is 4 units at a current of four times the current capacity of one unit cell. The failure of any unit cell in either a short-circuit mode or an open circuit mode will not prevent the array from providing current although the maximum available output voltage or current may be reduced.

[0056] Large arrays of unit cells can be constructed to provide large power- generating electrochemical cell layers in which the entire electrochemical structure is contained within the layer. This means additional components such as plates for collecting currents etc. can be eliminated, or replaced with structures serving different functions. Structures like those described herein are well adapted to be manufactured by continuous processes. Such structures can be designed in a way which does not require the mechanical assembly of individual parts. Unlike 'edge collected' cells, the conductive path lengths within this structure may be kept extremely short so that ohmic losses in the catalyst layer are minimized.

[0057] An electrochemical cell layer comprising a plurality of unit cells may be constructed by providing a substrate comprising a plurality of ion conducting regions. Such a substrate could be provided, for example by selectively treating a sheet of non- or partially-conducting material to form the ion conducting regions, or by selectively treating a sheet of ion conducting material to form non-conducting regions, as described, for example in the commonly-assigned application entitled "MICRO-STRUCTURED MEMBRANES AND ELECTROCHEMICAL CELLS INCORPORATING SUCH MEMBRANES" which is referred to above. Current- carrying structures may be formed on each side of the substrate around the periphery of each ion conducting region by means of laminating, PVD, sputtering, plating, or other suitable techniques. An electrochemical reaction layer, which may comprise a catalyst, may be deposited on each side of the ion conducting regions, in at least partial contact with the current-carrying structures.

[0058] Individual unit cells may be very small. Other factors being equal, smaller unit cells can operate at improved efficiencies because the conduction paths for protons and electrons can be shorter in small unit cells than in larger unit cells. The unit cells can be very small, for example, 1 mm in diameter or smaller, or even 500 μm in diameter or smaller. In some embodiments of the invention, unit cells have active areas of about e.g. 0.01 cm². A typical air breathing fuel cell comprising a 1 mm diameter unit cell may produce between about 1 and 3 mW of power. A fuel cell layer comprising 300-1000 such cells could produce 1 W of power.

[0059] An electrochemical cell according to this invention may have as few as 1 unit cell or may have a very large number, thousands or even millions, of unit cells formed on one substrate. Electrochemical cell structures made according to some prototype embodiments of this invention have in excess of 500 unit cells, for example.

[0060] So far, substrate 30 and membrane electrode assemblies generally have been described as being planar. This is not necessary. Unit cells according to the invention may be used in an electrochemical cell layer that is pleated or undulating as shown, for example, in Figure 9. Such layers are very compact. Substantially the entire undulating area can be made active. Further, no porous layer is required beyond the catalyst layer and no unsupported face seals are required. Thus the undulating area can be tightly pleated since there is no porous medium between the pleats to interfere with the diffusion of fuel and oxidant to the exposed catalyst layers of the unit cells. Unit cells according to the invention may be incorporated in a pleated layer structure as described, for example, in the commonly-assigned patent application entitled "ELECTROCHEMICAL CELLS FORMED ON PLEATED SUBSTRATES" filed concurrently herewith, which is hereby incorporated herein by reference.

[0061] Figures 10 and 10A show a fuel cell device 50 according to one embodiment of the invention. Fuel cell device 50 comprises a fuel cell layer 52 comprising a plurality of unit cells 54. Fuel cell layer 52 comprises a positive terminal 53 and a negative terminal 55, which may be connected to an external circuit (not shown). Unit cells 54 may be connected between positive terminal 53 and negative terminal 55 in any suitable manner. Fuel cell layer 52 is sealed to a spacer 56, which is in turn sealed to a base 58. Fuel cell layer 52, spacer 56 and base 58 define a plenum 60 for holding fuel, which may be introduced through fuel inlet 62. An optional fuel outlet 64 may be provided if fuel flow is required, or if recirculation of fuel is required. Base 58 could optionally be replaced with another fuel cell layer, oriented oppositely to layer 52. Also, spacer 56 could be built into layer 52, such that two such layers could be bonded back to back to form a fuel cell device having two fuel cell layers.

[0062] Figure 11 shows a non-planar fuel cell device 66 according to another embodiment of the invention. Device 66 is the same as device 50, except that fuel cell layer 68, spacer 70 and base 72 are curved. In the example illustrated in Figure 11, layer 68, spacer 70 and base 72 are shaped to conform to the wall of a cylinder, but it is to be understood that other non-planar configurations are equally possible.

[0063] Figure 12 shows a stack of fuel cell layers 52 and spacers 56 according to another embodiment of the invention. Plenums defined by spacers 56 may be filled with fuel and oxidant in alternating fashion to provide reactants to layers 52.

[0064] Some embodiments of the invention provide unit cells wherein an exposed area of a catalyst layer is greater than a cross sectional area of an ion- conducting layer through which ions liberated by reactions in the catalyst layer can pass through the cell. This can be seen, for example, in Figure 2D wherein a surface 124 of catalyst layer 24A has a surface area larger than a cross sectional area of the portion 125 of ion-conducting layer 25 through which ions (e.g. protons) generated in catalyst layer 24A pass to the opposing catalyst layer 24B. [0065] The invention also provides methods for operating electrochemical cells.

One such method comprises:

• providing an electrochemical cell having: a catalyst-containing electrochemical reaction layer having an outer face and an inner face; an electrical current- carrying structure underlying the electrochemical reaction layer at least in part; and an ion-conducting layer in contact with the inner face of the electrochemical reaction layer;

• allowing a reactant to diffuse into the electrochemical reaction layer;

• allowing the reactant to undergo a catalysed electrochemical reaction to produce an ion at a location in the electrochemical reaction layer between a surface of the electrochemical layer and the current-carrying layer; and, allowing the ion to travel to the ion-conducting layer along a path that avoids the current-carrying structure. The path taken by the ion is not substantially anti-parallel to a path taken between the by electrical current between the location and the current-carrying structure.

[0066] Where a component (e.g. a membrane, layer, device, circuit, etc.) is referred to above, unless otherwise indicated, reference to that component (including a reference to a "means") should be interpreted as including as equivalents of that component any component which performs the function of the described component (i.e., that is functionally equivalent), including components which are not structurally equivalent to the disclosed structure which performs the function in the illustrated exemplary embodiments of the invention.

[0067] In some embodiments of the invention, a filter layer may be provided on the outer surface of one or both of catalyst layers 24A, 24B. The filter layer may be used to remove undesired materials from reactants before they reach catalyst layer 24A or 24B. For example, a filter layer placed over the cathode catalyst layer may be impermeable to water but permeable to air, to allow air to reach the cathode of the unit cell, while preventing water from reaching the unit cell. Figure 13 illustrates an example of structure 20A wherein a filter layer 200 is provided on the outer surface of catalyst layer 24B.

[0068] It is noteworthy that in a number of the embodiments described above, electrical current from electrochemical reactions occurring in a catalyst layer is collected in the plane of the catalyst layer.

[0069] As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the spirit or scope thereof. For example: This invention has application to fuel cells as well as electrochemical cells of other types such as chlor-alkali reaction cells and electrolysis cells.

• The invention is not limited to gaseous fuels. Liquid fuels may also be used with appropriate material selections.

• The anodes and cathodes of the unit cells do not need to be the same size. The anodes may, for example, be somewhat smaller than the cathodes. Any exposed traces could be located on the anode side of the membrane electrode assemblies. • The catalyst layers are layers where electrochemical reactions occur. In some embodiments these layers may not comprise catalysts in the strict sense of the term. In some embodiments, the current-carrying structures are depicted as being in direct contact with the ion exchange membrane, but this is not necessary. It is to be understood that the current-carrying structures may be separated from the ion exchange membrane by another material, such as a portion of the catalyst layer. [0070] Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.

Claims

WHAT IS CLAIMED IS:

1. An electrochemical cell comprising: an ion exchange membrane; two electrochemical reaction layers located on opposite sides of the ion exchange membrane, each electrochemical reaction layer having an inner surface at least partially in contact with the ion exchange membrane, and an outer surface opposite the inner surface; and, two current-carrying structures located on opposite sides of the ion exchange membrane, each current-carrying structure having electrically- conducting portions in contact with one of the electrochemical reaction layers wherein the electrically conducting portion of at least one of the current- carrying structures is located inwardly from the outer surface of the associated electrochemical reaction layer.

2. An electrochemical cell according to claim 1 wherein the electrically conducting portion of both of the current-carrying structures are located inwardly from the outer surfaces of the associated electrochemical reaction layers.

3. An electrochemical cell according to claim 1 at least one of the current-carrying structures is in contact with the ion exchange membrane.

4. An electrochemical cell according to claim 3 wherein each of the current- carrying structures is positioned on a surface of the ion exchange membrane.

5. An electrochemical cell according to claim 3 wherein each of the current- carrying structures is embedded within a surface of the ion exchange membrane.

6. An electrochemical cell according to claim 1 wherein at least one of the current-carrying structures is positioned entirely inwardly from the outer surface of the associated electrochemical reaction layer.

7. An electrochemical cell according to claim 1 wherein a portion of at least one of the current-carrying structures extends outwardly past the outer surface of the associated electrochemical reaction layer.

8. An electrochemical cell according to claim 1 wherein the ion exchange membrane comprises a composite membrane.

9. An electrochemical cell according to claim 1 wherein the ion exchange membrane comprises an ion-conducting material deposited in an opening in a substrate.

10. An electrochemical cell according to claim 9 wherein the ion exchange membrane comprises at least one ion-conducting skin deposited on a surface of the ion-conducting material.

11. An electrochemical cell according to claim 9 wherein each of the current- carrying structures extends around a periphery of the opening.

12. An electrochemical cell according to claim 11 wherein each of the current- carrying structures is positioned on the substrate.

13. An electrochemical cell according to claim 9 wherein each of the current- carrying structures is positioned on the substrate.

14. An electrochemical cell according to claim 9 comprising an electrically- conducting pathway embedded in the substrate, the electrically-conducting pathway being electrically connected to one of the current-carrying structures.

15. An electrochemical cell according to claim 1 wherein the electrochemical reaction layers have thicknesses not exceeding 250 micrometers.

16. An electrochemical cell according to claim 15 wherein the electrochemical reaction layers have thicknesses of about 20 micrometers.

17. An electrochemical cell according to claim 1 wherein the ion exchange membrane has a thickness in the range of 5 to 250 micrometers.

18. An electrochemical cell according to claim 17 wherein the ion exchange membrane has a thickness of about 25 micrometers.

19. An electrochemical cell according to claim 1 wherein the current-carrying structures have thicknesses in the range of 5 to 75 micrometers.

20. An electrochemical cell according to claim 19 wherein the current-carrying structures have thicknesses in the range of about 25 to 50 micrometers.

21. An electrochemical cell according to claim 20 wherein the current-carrying structures have widths in the range of about 5 to 200 micrometers.

22. An electrochemical cell according to claim 1 wherein each of the current- carrying structures forms a closed path around a periphery of a region on a surface of the ion exchange membrane.

23. An electrochemical cell according to claim 22 wherein each of the current- carrying structures comprises a trace having one of a circular, elliptical, rectangular, hexagonal and polygonal shape.

24. An electrochemical cell according to claim 22 wherein the current carrying structures are symmetrically located with respect to the ion exchange membrane.

25. An electrochemical cell according to claim 1 comprising a filter layer positioned on the outer surface of at least one of the electrochemical reaction layers.

26. An electrochemical cell layer comprising a plurality of electrochemical cells according to claim 1.

27. An electrochemical cell layer according to claim 26 wherein the plurality of electrochemical cells are arranged in a regular array.

28. An electrochemical cell layer according to claim 26 wherein the plurality of electrochemical cells are connected in parallel.

29. An electrochemical cell layer according to claim 26 wherein the plurality of electrochemical cells are connected in series.

30. An electrochemical cell layer according to claim 26 wherein the plurality of electrochemical cells are connected in series-parallel.

31. An electrochemical cell layer according to claim 30 wherein the plurality of electrochemical cells comprise a number of groups of cells connected in series, the groups being connected in parallel.

32. An electrochemical cell layer according to claim 31 wherein each group comprises electrochemical cells which are spatially separated.

33. An electrochemical cell layer comprising a plurality of electrochemical cells according to claim 14, wherein the plurality of electrochemical cells are connected in series by the electrically-conducting pathway embedded in the substrate.

34. An electrochemical cell device comprising an electrochemical cell layer according to claim 26 sealed to a spacer which is in turn sealed to a base, wherein the electrochemical cell layer, the spacer and the base define a plenum.

35. An electrochemical cell device according to claim 34 wherein the electrochemical cell device comprises a fuel cell device, and the plenum is configured to hold fuel.

36. An electrochemical cell device according to claim 34 wherein the spacer comprises an inlet for introducing reactants into the plenum.

37. An electrochemical cell device according to claim 34 wherein the spacer comprises an outlet for removing products from the plenum.

38. An electrochemical cell device according to claim 34 wherein the spacer comprises an inlet and an outlet configured to allow materials to be introduced to and removed from the plenum.

39. An electrochemical cell having a current-carrying structure underlying a porous electrochemical reaction layer and adjacent to an ion conducting membrane.

40. An electrochemical cell according to claim 1 wherein the electrochemical cell has a hexagonal shape.

41. An electrochemical cell according to claim 1 wherein the cell has an elongated shape, the elongated shape having a longer dimension and a shorter dimension.

42. An electrochemical cell according to claim 41 wherein the longer dimension is at least twice the shorter dimension.

43. An electrochemical cell according to claim 41 wherein the elongated shape is an elongated rectangular shape.

44. An electrochemical cell according to claim 41 wherein the elongated shape is an elongated elliptical shape.

45. An electrochemical cell according to claim 41 wherein the elongated shape is an elongated obround shape.

46. A core assembly for an electrochemical cell, the core assembly comprising: an ion exchange membrane; an electrically conducting electrochemical reaction layer on at least a first side of the ion exchange membrane; and, an electrically-conductive current-carrying structure in electrical contact with the electrochemical reaction layer, wherein an outer surface of the electrochemical reaction layer overlies at least a portion of the current-carrying structure.

47. A core assembly according to claim 46 wherein the electrochemical reaction layer comprises a catalyst.

48. A method for operating an electrochemical cell, the method comprising: providing an electrochemical cell having: a catalyst-containing electrochemical reaction layer having an outer face and an inner face; an electrical current-carrying structure underlying the electrochemical reaction layer at least in part; and an ion-conducting layer in contact with the inner face of the electrochemical reaction layer; allowing a reactant to diffuse into the electrochemical reaction layer; allowing the reactant to undergo a catalysed electrochemical reaction to produce an ion at a location in the electrochemical reaction layer between a surface of the electrochemical layer and the current-carrying layer; and, allowing the ion to travel to the ion-conducting layer along a path that avoids the current-carrying structure.

49. A method of constructing an electrochemical cell layer, comprising: providing a substrate having a plurality of ion-conducting regions; forming a current-carrying structure around a periphery of each ion- conducting region on each side of the substrate; and, forming an electrochemical reaction layer in contact with each current- carrying structure and the associated ion-conducting region.

50. A method according to claim 49 wherein providing the substrate comprises selectively treating a sheet of non-conducting material to form the ion- conducting regions. A method according to claim 49 wherein providing the substrate comprises selectively treating a sheet of ion-conducting material to form the ion- conducting regions.