Classifications

• • 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
  • H01M8/08—Fuel cells with aqueous electrolytes
  • H01M8/083—Alkaline fuel cells
• • 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
  • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
  • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
• • 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
  • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
• • 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
  • H01M8/0263—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
  • H01M8/04—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
  • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
  • H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
• • 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
  • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged 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
  • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• This invention relates to alkaline fuel cells, and particularly to the flat electrode structures from which a stacked alkaline fuel cell is assembled.
• the present invention provides for the design of flat electrode structures for use in stacked alkaline fuel cells which permit efficient and low loss gas flow across gas diffusion electrodes, and the flow of circulating alkaline electrolyte, through the stacked alkaline fuel cell.
• Another feature of the present invention provides for improved electrode contact with considerably reduced risk of electrode buckling during thermal cycling of the stacked alkaline fuel cell.
• Alkaline fuel cells have been known, at least in rudimentary form, since shortly after the turn of the 20th century. Indeed, alkaline fuel cells have found at least limited success and acceptance because of their use by NASA, particularly since the Apollo missions. Alkaline fuel cells were also used by NASA for the space shuttle Orbiter vehicles. However, there has been much greater commercialization of Proton Electrode Membrane (PEM) fuel cells for a variety of reasons that need not be discussed in detail here.
• PEM Proton Electrode Membrane
• alkaline fuel cells can be manufactured without having to rely on precious or noble metal electrodes; and that the electrolyte is alkaline and not acidic, which leads to better electrochemical performance and generally broader operating temperatures than those of PEM fuel cells
• the general structure of alkaline fuel cells is quite simple.
• fluid channels are formed through the plastic electrode frames for the distribution of gas and electrolyte.
• the fuel gas is hydrogen, although it may also be such as methanol vapour
• the oxidizer gas is oxygen or air
• the electrolyte is alkaline solution such as aqueous potassium hydroxide solution.
• One purpose of any design of electrode frames for alkaline fuel cells is to provide for even distribution of the flow of gases across the faces of the electrodes.
• the prior art alkaline fuel cells have had problems relating to the elimination of droplets of moisture which develop in the gas path.
• Prior art alkaline fuel cells also have had difficulty with respect to thermal stresses that may be caused by uneven currents, typically because of uneven gas flow, among other contributing factors.
• the present invention seeks to overcome those and other shortcomings of prior art alkaline fuel cells by providing for even distribution of the flow of gases across the face of the electrodes, and by providing design features which effectively eliminate unwanted buildup of droplets of condensate which may be contaminated with electrolyte running down the face of the electrodes.
• the present invention also provides designs which reduce thermal stresses that may be caused by uneven currents as they flow through the electrode structures, and which are also caused by thermal cycling. That feature is particularly accomplished by the provision of a metal contact frame embedded in the plastic electrode frame so as not only to improve current collection in monopolar cells, but also so as to significantly reduce the thermal expansion of the plastic frame. This reduces stresses imposed on the electrode as well as stresses imposed on the inter-cell seal, and thereby contributes to improved tolerance of thermal cycling. This, in turn, provides for increased longevity of the stacked alkaline fuel cell structure.
• plastic frames for flat electrode structures for use in alkaline fuel cells are manufactured is beyond the scope of the present invention, except as will be described hereafter with respect to the stiffness, modulus of elasticity, and coefficient of thermal expansion, of that material. Suffice itto say that such material may be either a thermoplastic material or a thermosetting material.
• openings are formed through the thickness of the plastic frames so as to provide for passages which permit gas flow or electrolyte flow from one end of the stack structure to the other.
• a stacked alkaline electric fuel cell structure is assembled by placing flat electrode structures adjacent one to another, observing polarity of the electrodes being put into place, and securing them by such as adhesive, compression, welding and other well-known methods. Accordingly, such a stacked structure with openings in the plastic frames is said to have internal manifolding, as opposed to external manifolding, so that inlet and outlet conduits for gas and electrolyte can be connected to the entire stack structure.
• any liquid which finds its way into gas spaces of the cells must be promptly removed in order to assure good access of the gas to the working surface of the electrode.
• This has typically meant in prior art alkaline fuel cells that the gas would flow from top to bottom of each of the individual cells, so as to carry the liquid out of the cell in a manner which provides for the least hydraulic resistance to the flow of fluid, namely downwardly with the assistance of gravity.
• a typical prior art cell structure provided for flat, thin gas spaces in the individual cells, having one or a plurality of exit slits at the bottom of the cell.
• the problem has been that such bottom slits may become blocked by drops of liquid which remain in place as a consequence of capillary forces.
• the catalyst layer includes catalyst particles, a hydrophobic binder, and hydrophilic catalytically inactive particles, whereby a network of liquid transport pathway is provided through the catalyst layer.
• a flat electrode structure for use in alkaline fuel cell stacks, where the fuel cell stack comprises a plurality of flat electrode structures placed side-by-side so as to have electrolyte inlet and outlet manifolds, fuel gas inlet and outlet manifolds, and oxidizer gas inlet and outlet manifolds throughout the length of the stack.
• Each of the stacked flat electrode structures comprises a framed electrode having an electrode face for contact with the electrolyte and a respective one of the fuel gas or the oxidizer gas.
• the electrode is secured in a surround frame having top and bottom frame members and opposed side frame members.
• the electrolyte, fuel gas, and oxidizer gas manifolds are each respectively in fluid communication through the thickness of the frame members for external connection at the ends of the fuel cell stack to respective electrolyte, fuel gas, and oxidizer gas conduits.
• each flat electrode structure is formed through the thickness of the bottom frame member, and the electrolyte outlet manifold is formed through the thickness of the top frame member.
• the electrolyte inlet and outlet manifolds are in fluid communication with the electrode face through electrolyte flow channels formed in the surface of the top and bottom frame members at the same side of the electrode structure where the electrode face is located.
• two electrolyte flow channels are formed in each of the top and bottom frame members so as to be in fluid communication with respective top and bottom corners of the respective electrode face.
• Gas flow channels are formed in the surface of each of the side frame members of each flat electrode structure, so as to provide fluid communication between the respective electrode face and the respective fuel gas inlet and outlet manifolds or oxidizer inlet and outlet manifold.
• side-to-side gas flow of the respective fuel gas or oxidizer gas across the electrode face is effected.
• the flat electrode structure may be such that the electrolyte flow channels are straight.
• the electrolyte flow channels may follow a convoluted path from the respective corners of the electrode face to the respective electrolyte inlet or outlet manifold.
• the convoluted path of the electrolytic flow channels is serpentine.
• the convoluted path of the electrolyte flow channels may be configured so as always to accommodate an upward flow of electrolyte and thereby so as to preclude the development of gas lock caused by trapped gas bubbles in the liquid column of electrolyte within the electrolyte flow channels.
• the gas inlet and outlet manifolds are formed in each of the side frames, and their respective gas flow channels, are arranged in such a manner that there is fluid communication among the gas flow channels in one of the side frame members to the gas flow channels in the other of the side frame members.
• the flat electrode structure may be such that there are at least two gas inlet and outlet manifolds formed in each of said side frame members, and they are arranged in alternative order; or they may be arranged in adjacent groups.
• each of the gas flow channels has a height substantially equal to the height of the respective gas inlet or outlet manifold with which it is in direct fluid communication adjacent that respective gas inlet or outlet manifold, and has a greater height than the height of the respective gas inlet or outlet manifold at the end of the gas flow channel adjacent the electrode face.
• each of the gas inlet and outlet manifolds may be essentially rectangular, having greater height than width. Moreover, the corners of each of said gas inlet and outlet manifolds are typically rounded.
• each of the top and bottom frame members and each of the opposed side frame members are formed of a plastic material.
• a metal conductive foil member embedded in the plastic frame members so as to form a continuous embedded metal contact frame surrounding the electrode face and being in electrically conductive relationship to the current collector member.
• the moduli of elasticity of the plastic material of the plastic frame members, and of the metal conductive foil member are such that the metal material of the metal conductive foil member is typically at least 10 times or more stiffer than the plastic material of the plastic frame.
• the plastic material of the plastic frame member may include a filler chosen from the group consisting of talc, alumina, silica, glass, kaolin, kaolinite, calcite, carbon, ceramic fillers, and mixtures thereof.
• FIG. 1A and Figure 2B show alternative configurations of electrolyte flow channels, it being understood that the other end of the flat electrode structures of those figures is identical to the end which is shown;
• Figure 3 is an elevation of another typical flat electrode structure in keeping with the present invention, showing a typical arrangement of gas flow manifolds and their associated gas flow channels;
• Figure 4 is an elevation of a further typical flat electrode structure having an alternative arrangement of gas flow manifolds and their associated gas flow channels;
• Figure 5 is an elevation view of a further typical flat electrode structure in keeping with another feature of the present invention whereby deformation as a consequence of thermal cycling is alleviated.
• FIG 1 a first typical embodiment of a flat electrode structure which is suitable for use in alkaline fuel cells is shown at 12.
• Other typical embodiments of flat electrode structures which are suitable for use in alkaline fuel cells are shown at 14 in Figure 2A and 16 in Figure 2B.
• the same reference numerals are used throughout all of the figures of drawings which are described hereafter to indicate the same feature of the flat electrode structures being discussed at any time.
• Figures 1 , 2A, and 2B are intended only to show representative electrolyte inlet and outlet manifolds and electrolyte flow channels; and likewise, the embodiments shown in Figures 3 and 4 are intended only to show typical arrangements of fuel gas and oxidizer gas inlet and outlet manifolds and their associated gas flow channels. In other ⁇ words, each of those figures has been highly'simplified for purposes of clarity and illustration only.
• Each flat electrode structure comprises a framed electrode which is shown generally at 20.
• the electrode structure is rectangular.
• the specific features, chemistry, and structure, of the electrodes 20 are outside the scope of this present invention. While electrolyte flow from the bottom to the top of the cell is known, the inventor herein has quite unexpectedly discovered that better and more efficient fuel cell operation is achieved when the gas flow of the fuel gas and oxidizer gases is horizontal, that is from side to side of each respective cell, across the electrode face of that cell. This is described in greater detail hereafter.
• each electrode will have a working face that is designed in keeping with well known principles to interact with the electrolyte or the respective fuel gas or oxidizer gas.
• Each electrode frame which surrounds the electrode has top and bottom frame members 22 and 24, and opposed side frame members 26 and 28. Located in the top frame member 22 is the electrolyte outlet manifold 32, which is formed through the thickness of the electrode frame. The electrolyte inlet manifold 34 is formed in the bottom frame member 24.
• electrolyte flow channels Two inlet channels 36 are formed in each of the top and bottom frame members 22, 24, and are referred to herein as electrolyte flow channels. It will be seen that the electrolyte flow channels are in fluid communication across the electrode face through flow channel faces 40. It will also be seen that the electrolyte flow channels communicate to the respective inlet and outlet manifolds 34 and 32 from the corners of the electrode face. Because an electrolyte flow within the cell is achieved as a consequence of both pumping and convection flow, wetting of the entire electrode face is assured. It will also be understood that the corner exits for the electrolyte into the electrolyte flow channels will help in the easy removal of entrained gas bubbles within the liquid electrolyte, even if the cell is leaned out of its vertical position.
• electrolyte flow channels which are connected to common manifolds may present paths for parasitic currents.
• the resistance of the electrolyte channels should be reasonably high.
• the electrical resistance of the liquid column of electrolyte within an electrolyte flow channel is directly proportional to the length of the flow channel and inversely proportional to its cross-section.
• there may also be hydraulic considerations which limit the design choice as to how small the electrolyte flow channels may be, so it may be considered to be desirable to increase the length of the electrolyte flow channels by arranging them in a convoluted path.
• that path may be serpentine, as shown at flow channels 36A in Figure 2A, and flow channels 38B in Figure 2B.
• flow channels 36A in Figure 2A and flow channels 38B in Figure 2B.
• the opposite ends of the electrodes 14 and 16 shown in Figures 2A and 2B, respectively, will be the same as the end which is shown.
• the specific difference between the electrolyte flow channels 36A and 38B is that channels 38B are nearly twice as long as channels 36A. In any event, all of the electrolyte flow channels are in fluid communication with the respective electrolyte inlet and outlet manifolds 34 and 32.
• any of the electrolyte flow channels is such that there is always an upward flow of electrolyte through the respective electrolyte flow channel so as to thereby preclude the development of any gas lock which might occur as a consequence of trapped gas bubbles in the liquid column of electrolyte within the electrolyte flow channels.
• Figure 3 another typical configuration for a flat electrode structure in keeping with the present invention is shown. Here, for purposes of simplicity and clarity, consideration has not been given to the electrolyte flow channels and their respective inlet and outlet manifolds.
• the configuration of the embodiment of Figure 3 comprises the same top and bottom frame members 22, 24 and side members 26, 28, which surround the electrode 20. What is shown in this figure particularly is gas flow of the fuel gas, which is the consumable fuel for the stacked alkaline fuel cell.
• the fuel gas which is the consumable fuel for the stacked alkaline fuel cell.
• Gas flow across the face of the electrode 20 is seen to be from right to left as shown by arrows 50 in this illustrative embodiment.
• Figure 3 shows the fuel gas inlet and outlet manifolds and the oxidizer gas inlet and outlet manifolds being arranged in alternative order. That is, between a pair of fuel gas inlet manifolds 46 there is formed through the thickness of the right side frame 28 an oxidizer gas outlet manifold 58.
• Inspection shows the same arrangement on the left side frame 26, but in the reverse order so that the topmost manifold formed through the thickness of the left side frame member 26 is an oxidizer gas inlet manifold, and the topmost manifold formed through the thickness of the right side frame member 28 is a fuel gas inlet manifold, with the bottommost manifolds formed through the thicknesses of the left and right side frame members 26 and 28 being a fuel gas outlet manifold and an oxidizer gas outlet manifold, respectively.
• the inlet and outlet gas manifolds for the fuel gas and for the oxidizer gas is shown.
• the two fuel gas inlet manifolds 46 are shown as being adjacent to one another in the right side frame member 28, and the two oxidizer gas outlet manifolds 58 are also shown as being adjacent one to another in the right side frame member 28.
• a similar arrangement is made in the left side frame member 26 for the oxidizer gas inlet manifolds 56 and the fuel gas outlet manifolds 48. Otherwise, the same principles apply as to the functionality of the structure as it relates to both the electrolyte flow manifolds and the gas flow manifolds.
• gas flow channels 60 and 62 which, in this case, are the gas flow channels which provide for fuel gas flow from the fuel gas inlet manifolds 46 to the fuel gas outlet manifolds 48. It will be understood, once again, that there is fluid communication among the inlet fuel gas flow channels 60 and the outlet fuel gas flow channels 62, and that the fuel gas flow is essentially linear and laminar across the electrode face.
• each of the gas flow channels provides diffuser effect. This is accomplished by having the height of the gas flow channels to be essentially the same as the height of the respective gas flow manifold with which they are in direct fluid communication. However, the other end of each of the gas flow channels which is adjacent the electrode face has a greater height than the manifold end of the gas flow channels. This has the salutary effect of providing for a more evenly distributed gas flow across the entire height of the electrode face, while reducing the exit pressure and speed of the fuel gas or oxidizer gas as they flow from the respective gas inlet manifolds 46 or 56.
• the gas flow channels as shown in Figure 4 accommodates the arrangement where the inlet and outlet gas manifolds are arranged in adjacent pairs, which simplifies the design of the end plates for the stack of flat electrode structures in keeping with the present invention.
• the depth of the gas flow channels as they are formed in the faces of the respective side frame members of the electrode structures in keeping with the present invention may be in the range of from 0.5 to 1.0 mm.
• the increased height of the gas flow channels in the area in adjacent the electrode face will be understood to effect gas flow in a favorable manner.
• any liquid which may collect and be retained in the gas flow channels as a consequence of capillary action will, in any event, sit at the bottom of the gas flow channel. Because the gas flow is directed horizontally, what liquid may be collected and retained will be at the bottom of the channels; and it will be understood that the height of the channels will be significantly greater than the "capillary elevation" which is a function of the wetting properties of the liquid on the capillary wall and the dimensions of the capillary. In practical terms, this means that all of the manifolds with the exception of the two lowest outlet manifolds will remain dry and unobscured most of the time.
• the plastic material of the frame which surrounds the electrode may exhibit several times higher coefficient of thermal expansion than the electrode material itself. It will be seen, therefore, that changes of temperature during thermal cycling could lead to stressing the bond and seal between the electrode and the frame, which in turn would eventually lead to cracks in the electrode or buckling of the electrode, and in any event to premature failure. It will be kept in mind that the relative strength of the frame is much greater than that of the rather delicate mesh in the electrode, so that stretching of the electrode at increased temperature beyond its limit of elasticity would lead to buckling when the electrode cools.
• FIG. 5 shows an electrode structure 74 having a configuration which is, in general, similar to that of Figure 4.
• this electrode structure further includes a conductive metal foil member 76, which is typically copper but may be other electrically conductive metals, and which is embedded within the plastic frame member 22, 24, 26, 28. It will be seen that the conductive foil metal member 76 is a continuous embedded metal contact frame which surrounds the electrode face.
• the embedded metal contact frame is in electrically conductive relationship to the current collector member of the electrode 20, and is attached thereto by such means as spot welding, soldering, swaging, and so on as is well known to those skilled in the art.
• the presence of the continuous embedded metal contact frame 76 provides for much improved current collection and reduced resistive losses.
• the presence of the continuous embedded metal contact frame 76 provides for improved mechanical stability during thermal cycling, thereby resulting in reduced wear and longer life.
• the modulus of elasticity of the metal contact material is 1.15 x
• the modulus of elasticity of the plastic material of the frame is 0.018 x 10 6 kg/cm 2 .
• the coefficient of thermal expansion of the plastic material is 70 ppm/degree C; and the coefficient of thermal expansion of the metal material is approximately 16 ppm/degree C. Even if the metal and plastic materials were to be warmed up by 1 0 C, then the metal will increase its length by approximately 16 ppm, while the plastic will increase its length by approximately 70 ppm.
• the continuous metal contact frame 76 is embedded in the plastic frame member 22, 24, 26, 28, they are bonded one to the other. Thus, the metal will restrict the elongation of the plastic, and the plastic will pull or to try to stretch the metal, until such time as they reach a compromise or equilibrium.

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• Life Sciences & Earth Sciences (AREA)
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• General Chemical & Material Sciences (AREA)
• Fuel Cell (AREA)

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• 2006
  • 2006-03-06 EP EP06705284A patent/EP1997172A1/de not_active Withdrawn
  • 2006-03-06 WO PCT/CA2006/000331 patent/WO2007101318A1/en active Application Filing
  • 2006-03-06 CA CA002644201A patent/CA2644201A1/en not_active Abandoned

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