WO1998045503A1 - Electrolyse de saumures d'halogenures de metaux alcalins effectuee au moyen de systemes cathodiques comprenant de l'oxygene - Google Patents

Electrolyse de saumures d'halogenures de metaux alcalins effectuee au moyen de systemes cathodiques comprenant de l'oxygene

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Publication number
WO1998045503A1
WO1998045503A1 PCT/US1998/006769 US9806769W WO9845503A1 WO 1998045503 A1 WO1998045503 A1 WO 1998045503A1 US 9806769 W US9806769 W US 9806769W WO 9845503 A1 WO9845503 A1 WO 9845503A1
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WO
WIPO (PCT)
Prior art keywords
cathode
alkali metal
membrane
layer
compartment
Prior art date
Application number
PCT/US1998/006769
Other languages
English (en)
Inventor
Richard D. Varjian
Robert D. Mussell
Paul J. Gubanich
Original Assignee
The Dow Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to EP98914515A priority Critical patent/EP0979318A1/fr
Priority to AU68854/98A priority patent/AU727997B2/en
Priority to CA002286175A priority patent/CA2286175A1/fr
Publication of WO1998045503A1 publication Critical patent/WO1998045503A1/fr

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Classifications

    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells

Definitions

  • This invention relates to a process for the electrolysis of an alkali metal halide brine in an electrolytic cell, more particularly, to the use of oxygen cathode membrane assemblies for chlor- alkali electrolytic cells and to the use of flow field structures adjacent thereto.
  • Chlor-alkali electrolytic cells electrochemically convert alkali metal halide brine solutions into halogen gas and alkali metal hydroxides.
  • One type of chlor-alkali electrolytic cell typified by U.S Patent No. 4,191,618 to Coker et al. (“the '618 patent”) employs a membrane electrode assembly (“MEA”) including a membrane and an oxygen depolarized cathode attached thereto such that a unitary structure is formed.
  • the membrane itself serves as an electrolyte.
  • the cathode is an electroconductive catalytic material bonded to the membrane.
  • the catalyst layer is preferably covered by a porous hydrophobic layer to deter the formation of a water film over said electrode which might prevent the penetration of oxygen to the electrocatalyst. While the '618 patent was an improvement over the prior art, improvements of only 0.5 to 0.6 volts were reported, probably in part due to the buildup of caustic material at the electrode.
  • One aspect of the present invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell having an anode compartment having at least one anode, a cathode compartment having at least one cathode, and a membrane in contact with the cathode (thereby forming a membrane electrode assembly) which separates the anode compartment from the cathode compartment.
  • the method comprises (a) feeding the alkali metal halide brine to the anode compartment; (b) electrolyzing the alkali halide brine to produce a halogen gas and alkali metal ions; (c) passing the alkali metal ions and water through the membrane into the cathode compartment; and (d) feeding an oxygen-containing gas to the cathode compartment so that the oxygen is reduced at the cathode and a concentrated alkali metal hydroxide solution is produced.
  • the process is further characterized by having a flow field located adjacent to the cathode to facilitate transporting the oxygen gas to the cathode and alkali metal hydroxide away from the cathode and in that the flow field comprises an electrically conductive material having a porosity of at least 30 percent and a mean pore size of at least 10 microns.
  • Another aspect of the present invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell wherein the membrane comprises at least one active layer on the cathode side thereof, and wherein the active layer comprises (a) catalytically active particles and (b) an ionomer having an equivalent weight in the range of from 650 to 950 and which is substantially insoluble in water at a temperature of less than 100°C.
  • Another aspect of the invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell
  • the membrane-cathode assembly further includes a flow field adjacent to the active layer which comprises a layer of an electrically conductive porous material which has at least two portions with different mean pore sizes, wherein a first portion of the layer adjacent to the membrane electrode assembly has a porosity no greater than the second portion of the layer adjacent to the opposite side from the membrane electrode assembly; and wherein the second portion has a porosity of at least 30 percent; and the second portion has mean pore size which is at least 4 microns and at least two times greater than the mean pore size of the first portion.
  • Still another aspect of this invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell wherein the cathode comprises at least two layers of catalytically-active particle containing ink on one side of the membrane, wherein at least two layers of the catalytically-active particle containing ink comprise polytetrafluroethylene polymers having pendant sulfonic acid groups, equivalent weights which differ by more than 50.
  • Figure 1 illustrates one embodiment of the membrane electrode assembly and the flow field useful in the electrolytic cell of the first aspect of the invention.
  • Figure 2 illustrates one configuration of a repeat unit which may be utilized in the preparation of an electrolytic cell stack containing a plurality of electrolytic cells arranged in series, which incorporates the membrane electrode assembly and flow field illustrated in Figure 1.
  • Figure 3 illustrates a membrane electrode assembly having two active layers positioned on the same side of the membrane.
  • Figure 4 illustrates a membrane electrode assembly having a porous layer and a flow field adjacent thereto.
  • FIGS 5 and 6 depict the performance of the cells prepared in Examples 1 and
  • Figure 7 shows the experimental setup described in Example 1.
  • this invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell having a membrane electrode assembly and a flow field adjacent thereto wherein the flow field comprises an electrically conductive porous material having a porosity of at least 50 percent and a mean pore size of at least 35 microns.
  • the electrolytic cell of the first aspect of the invention is able to operate at relatively high current densities and relatively low cell voltages at lower gas flow rates.
  • the membrane and the layer of polymer containing metal catalytically-active particles must be hydrated in order to be sufficiently ionically conductive.
  • water passes from the anode compartment through the membrane to the cathode. Water may also be present due to the humidification of the oxygen-containing feed gas.
  • the efficiency of the electrolytic cell is reduced, since diffusion of gas through liquid water is slow relative to its diffusion through water vapor.
  • the porosity and pore size characteristics of the flow field in the electrolytic cell of the first aspect of the invention are believed to improve the mass transfer capabilities, which results in lower cell voltages at high current densities. It is believed, without intending to be bound by any particular theory, that the relatively high porosity and large pores combine to preserve effective gas transport in the presence of liquid water. Because the feed gas flow is in the plane of the flow field and substantially parallel to the active layer, the liquid is swept away from the active layer and out of the flow field by the gas stream, thus keeping pores open for effective transport of reactant gas to the catalytically-active particles.
  • this invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell having a membrane electrode assembly which comprises a solid polymer electrolyte, and at least two active layers positioned on at least the cathode side of the membrane; wherein the active layers comprise catalytically-active particles and an ionomer; the average equivalent weights of the ionomers in the layers differ by at least 50.
  • One or more additional active layers may be positioned between the first and second active layers.
  • this invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell having a membrane electrode assembly having a solid polymer electrolyte, and at least one active layer positioned on one side of the membrane; wherein the active layer comprises (a) catalytically-active particles, and (b) an ionomer having an equivalent weight in the range of from 650 to 950 and which is substantially insoluble in water at temperatures of less than 100°C.
  • membrane electrode assemblies of the second and third aspects of the invention when utilized in an electrolytic cell, provide a relatively low cell voltage at a given current density and gas flow rate.
  • the equivalent weight of the ionomer is believed to affect the water content of the active layer. It is believed, without intending to be bound by any particular theory, that the lower equivalent weight ionomer maintains a higher water content at low current densities. This higher water content improves the conductivity and the accessibility of the catalytically active particles, thereby decreasing the cell voltage. However, this increase in water content can lower the performance (increase cell voltage) at higher current densities. It has been discovered that the performance at both high and low current densities may be optimized by using a multi-layer active layer with a different equivalent weight ionomer in each layer. It is believed, without intending to be bound by any particular theory, that the improved performance results from the differences in hydrophilicity between the layers.
  • the lower equivalent weight ionomer is believed to provide an area within the MEA having a high water content, for better performance at low current densities, while the less hydrophilic higher equivalent weight ionomer helps transport water away from the membrane at higher current densities.
  • the use of a relatively low equivalent weight ionomer gives better performance at lower current densities.
  • this invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell having a membrane electrode assembly and a layer of an electrically conductive porous material adjacent thereto which has at least two portions with different mean pore sizes, wherein a first portion of the layer adjacent to the membrane electrode assembly has a porosity no greater than a second portion of the layer adjacent to the opposite side of the layer; the second portion has a porosity of at least 82 percent; and the second portion has a mean pore size which is at least 10 microns and at least ten times greater than the mean pore size of the first portion.
  • this invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell having a membrane electrode assembly with a nonwoven porous layer of an electrically conductive porous material adjacent thereto which has at least two portions with different mean pore sizes, wherein a first portion of the layer adjacent to the membrane electrode assembly has a porosity no greater than a second portion of the layer adjacent to the opposite side of the layer; the second portion has a porosity of at least 50 percent; and the second portion has a mean pore size which is at least 35 microns and at least ten times greater than the mean pore size of the first portion.
  • the present invention is a process for the electrolysis of an alkali metal halide brine in an electrolytic cell having an anode compartment having at least one anode, a cathode compartment having at least one cathode, and a membrane in contact with the cathode (thereby forming a membrane electrode assembly or MEA) which separates the anode compartment from the cathode compartment.
  • MEA membrane electrode assembly
  • the method comprises (a) feeding the alkali metal halide brine to the anode compartment; (b) electrolyzing the alkali halide brine to produce a halogen gas and alkali metal ions; (c) passing the alkali metal ions and water through the membrane into the cathode compartment; and (d) feeding an oxygen-containing gas to the cathode compartment so that the oxygen is reduced at the cathode and a concentrated alkali metal hydroxide solution is produced.
  • the process preferably further includes humidifying the oxygen-containing gas prior to feeding it into the cathode compartment. This can be done by bubbling the gas through water.
  • the cathode can operate at any temperature from ambient to the boiling point of the alkali metal hydroxide solution, and in general, higher temperatures are preferred.
  • the temperature of the water bubbler should exceed the cell temperature by at least 10°C. When the water bubbler temperature exceeds the cell temperature, the water vapor content of the oxidant gas is increased beyond the equilibrium content at the cell temperature. It is believed that in this situation water vapor will condense on the cathode solubilizing the alkali metal hydroxide, thereby increasing the removal rate of the alkali metal hydroxide and minimizing the possibility that alkali metal hydroxide will crystallize within the porous structure of the active layer or backing layer.
  • membrane electrode assembly (1) as used herein refers to the combination of the solid polymer electrolyte (also referred to herein as a “membrane") and catalytically-active particles in the electrolytic cell assembly, regardless of its configuration or method of preparation.
  • the layer of membrane material containing such particles are referred to as the "active layer”, regardless of whether such particles are incorporated into a discrete layer of polymer (2) and applied or laminated to the surface of the membrane (3), or incorporated into the membrane itself.
  • the flow field (4) is a layer of an electrically conductive porous material having a gas stream inlet and outlet connected thereto.
  • the flow field may comprise porous carbon material.
  • the electrolytic cell for use in the first aspect of the invention preferably contains no impermeable flow field components having engraved, milled, or molded flow channels configured across its entire active face. These channels deliver gases directly to the active layer through a porous carbon "backing layer" which supports the active layer, as illustrated in Figures 1 and 4 of U.S. Patent 5,108,849.
  • the flow field, bipolar plates, and/or end plates used as supports for the electrolytic cell and to separate cells in a multi-cell configuration may contain one or more ducts therein to increase the flow of reactant gases to the flow field in the electrolytic cell of the first aspect of the invention.
  • An example of such ducts is illustrated in Figure 2.
  • the flow field may have interdigitated channels cut into it to lower the pressure drop introduced into the reactant gases.
  • the porous carbon material may be treated with a perfluorosilane or fluorine composition to increase its hydrophobicity, or oxidized, sulfonated, or coated with a hydrophilic material to increase its hydrophilicity.
  • the conductivity of the flow field layer in the first aspect of the invention is preferably at least 0.01 Siemens/cm (S/cm), more preferably at least 0.1 S/cm, and most preferably at least 0.2 S/cm.
  • the preferred thickness of the flow field will depend on the optimal pressure drop across the flow field, but is preferably at least 1 mil( 0.02 mm), more preferably at least 5 mils (0.13 mm), and is most preferably at least 10 mils (0.25 mm); but is preferably no greater than 250 mils (6.35 mm), more preferably no greater than 100 mils (2.54 mm), and is most preferably no greater than 50 mils (1.27 mm).
  • the porosity of the flow field is preferably at least 75 percent, more preferably at least 80 percent.
  • the mean pore size of the flow field is preferably at least 45 microns, more preferably at least 50 microns; but is preferably no greater than 1000 microns, more preferably no greater than 250 microns.
  • the term "mean pore size" as used herein means that half the open volume of the material is contained in pores larger in diameter than the mean pore size, and half is contained in pores equal to or smaller than the mean pore size.
  • the mean pore size may be measured by any convenient method, such as by mercury porosimetry.
  • the device used to measure the mean pore size distribution of the layer may be calibrated using silica alumina calibration standards (available from Micromeritics, Norcross, GA).
  • a layer of a catalyst "ink” is first applied to a solid polymer electrolyte, a carbon fiber paper, or a release substrate.
  • Catalyst inks typically comprise catalytically-active particles (such as platinum supported on carbon), binder, solvent or dispersing aid and, optionally, a plasticizing agent.
  • the ink comprises catalytically-active particles, and at least one compound which functions as an ionomer, such as a polytetrafluoroethylene polymer having sulfonic acid groups and an equivalent weight (based on the acid groups) in the range of from 650 to 1400.
  • the ink also preferably contains an organic solvent or dispersing aid which permits the application of a thin, uniform layer of the catalyst/ionomer mixture to the solid polymer electrolyte, carbon fiber paper, or release substrate.
  • a layer of catalyst "ink” is first applied to a solid polymer electrolyte, and then a layer of a second and third ink is applied to the portion of the MEA located opposite the first active layer or to a release substrate, or on top of the first active layer.
  • active layer refers to a layer comprising a mixture of ionomer and catalytically-active particles.
  • the MEA useful in the electrolytic cell of the first aspect of the invention may be prepared by any suitable method, but is preferably prepared by applying the catalyst ink (a suspension or dispersion of the catalytically-active particles) directly to a solid polymer electrolyte as described, for example, in U.S. Patent 5,211,984.
  • the ink is applied to the membrane in one or more applications sufficient to give a desired loading of catalytically- active particles.
  • the layer of catalytically-active particles is prepared by applying at least two inks in separate steps to form layers of the different inks.
  • the membrane electrode assembly comprises a solid polymer membrane having at least two layers of catalyst ink on at least one side thereof, wherein at least two layers of the catalyst ink comprise polytetrafluoroethylene polymers having pendant sulfonic acid groups, the equivalent weights of which differ by more than 50.
  • the MEA is positioned next to the flow field in the electrolytic celLassembly.
  • the electrolytic cells described herein may be incorporated in a multi-cell assembly or "stack" comprising a number of electrolytic cells arranged in series.
  • FIG. 2 An example of a repeat unit is illustrated in Figure 2, which shows a macroporous anode support (5), an MEA (6), a cathode flow field (7), and a bipolar separator plate (8).
  • the bipolar separator plate has ducts (9) and (10) which transport the reactants and reaction products to and from the flow field.
  • the porous cathode flow field has an inert material impregnated into the border regions (the darker areas in the figure) in order to prevent the reactants and products from escaping to the outside.
  • the border of the macroporous anode support should be solid or filled so it can deter or prevent leaks.
  • the material used to prepare the bipolar plate separator may be selected from a variety of rigid or nonrigid materials, and the plate has gas delivery ducts molded or embossed into its surface. These ducts deliver feed gas to, and remove reaction products from, the porous flow fields. In an alternative embodiment, gases and products may be introduced or removed via ducts or open spaces in the porous flow field connected to manifolds.
  • the bipolar separator plate may also have an internal structure for circulating a cooling fluid therein.
  • the first active layer is preferably first dried sufficiently before application of the second ink to prevent too much mixing of the inks.
  • a minor degree of mixing of the inks at their point of contact with each other may be desirable since it will promote electrical and ionic conductivity between the active layers.
  • they are preferably heated under conditions sufficient to volatilize at least 95 percent of any organic solvent or dispersing aid present in the inks.
  • solid polymer electrolyte refers to a porous layer comprised of a solid polymer which has a conductivity of at least 1 x 10 " Siemens/cm (S/cm) under the operating conditions of the electrolytic cell, or which may be reacted with acid or base to generate a porous layer having such conductivity.
  • the solid polymer electrolyte comprises a film of a sulfonated fluoropolymer, or a layered composite of films of sulfonated fluoropolymers having different equivalent weights. In chlor-alkali cells sulfonated membranes are preferred when the catholyte caustic strength is less than 20 percent.
  • a bi-layer membrane sulfonated polymer adjacent to the anolyte; carboxylated polymer adjacent to the catholyte.
  • the carboxylated polymer has a higher electrical resistance but greater hydroxyl ion rejection. Therefore it is preferred that the carboxylated polymer layer is normally thinner than the sulfonated polymer layer in the bi-layer configuration.
  • the ink After application of a catalyst ink to a solid polymer electrolyte, the ink is preferably heated under conditions sufficient to remove enough of the organic solvent or dispersing aid so that the active layer comprises at least 99 percent by weight, more preferably at least 99.9 percent by weight of the mixture of catalytically-active particles and the ionomer.
  • the ink is applied in an amount sufficient to provide a layer of the mixture which has a thickness of at least 1 ⁇ m, more preferably at least 5 ⁇ m, and most preferably at least 10 ⁇ m; but is preferably no greater than 30 ⁇ m.
  • the porosity of the layer is preferably at least 30 percent, more preferably at least 50 percent; but is preferably no greater than 90 percent, more preferably no greater than 60 percent.
  • the mean pore size of the layer is preferably at least 0.01 ⁇ m, more preferably at least 0.03 ⁇ m; but is preferably no greater than 10 ⁇ m, more preferably no greater than 0.5 ⁇ m, and is most preferably 0.1 ⁇ m.
  • the thickness, porosity, and pore size characteristics referred to above refer to measurements taken when the ionomer(s) contained in the layer are in their dry and protonated form.
  • the components of the MEAs useful in the second and third aspects of the invention are assembled by positioning one of the active layers in contact with the solid polymer electrolyte, and then positioning the second and third active layer so that it is between the first active layer and the porous carbon material, forming the membrane/electrode assembly thereby.
  • catalytically-active particles refers to particles of a metal or compound which are catalytic for the electroreduction of oxygen under the pressure and temperature conditions in the electrolytic cell.
  • particles which are useful include particles of platinum, ruthenium, gold, palladium, rhodium, iridium, electroconductive and reduced oxides thereof, and alloys of such materials, either in combination with each other or with other transition metals.
  • Other possible catalysts include but are not limited to: silver, manganese oxide, transition metal centered macrocyclic molecules such as cobalt porphryn and cobalt phthalocyanine, and transition metal macrocyclic molecules heated in nitrogen to 700°C.
  • the particles may be supported on a suitable material, if desired, such as carbon black.
  • the catalytically-active particles are platinum particles supported on carbon, which preferably contain from 10 percent to 30 percent by weight of platinum.
  • the size of the catalytically-active particles (on an unsupported basis) is preferably at least 10 A, more preferably at least 20 A; but is preferably no greater than 500 A, more preferably no greater than 200 A. Larger size particles may also be utilized, or may form during cell operation by the agglomeration of smaller particles. However, the use of such particles may result in decreased cell performance.
  • the catalytically-active particles are preferably used in an amount sufficient to provide an optimum catalytic effect under the operating conditions of the electrochemical device in which they are employed.
  • they are utilized in an amount sufficient to provide a loading level on the cathode side of the membrane of at least 0.01 mg/cm 2 , more preferably at least 0.1 mg/cm " , and is most preferably at least 0.15 mg/cm ; but is preferably no greater than 0.5 mg/cm , more preferably no greater than 0.35 mg/cm , and is most preferably no greater than 0.25 mg/cm 2 .
  • Catalysts such as silver, manganese oxide, transition metal centered macrocyclic molecules such as cobalt porphryn and cobalt phthalocyanine, and transition metal macrocyclic molecules heated in nitrogen to 700°C, may optimally be used in an amount sufficient to provide a loading level of up to as much as 5 mg/cm 2 .
  • Suitable organic compounds for use in the preparation of the catalyst ink include polar solvents such as glycerin, C ⁇ _ 6 alcohols, and other compounds such as ethylene carbonate, propylene carbonate, butylene carbonate, ethylene carbamate, propylene carbamate, butylene carbamate, acetone, acetonitrile, difluorobenzene, and sulfolane, but is most preferably propylene carbonate.
  • the organic compound is preferably present in an amount, based on the weight of the composition, of at least 10 percent, more preferably at least 20 percent, and is most preferably at least 30 percent; but is preferably no greater than 90 percent.
  • solvents in the ink function primarily as solvents or dispersing aids.
  • Suitable ionomers for use in the preparation of the catalyst inks described herein include any polymer or oligomer having an ionic conductivity of at least 1 x 10 " S/cm, more preferably at least 10 "1 S/cm (under the operating conditions of the electrolytic cell), or which may be reacted with acid or base to generate an oligomer or polymer having ionic conductivity.
  • suitable ionomers include fluoropolymers having pendant ion exchange groups, such as sulfonic acid groups in proton or salt form.
  • Examples of such include sulfonic fluoropolymers having fluoropolymer backbones and 1 to 5 carbon atom pendent ion exchange groups attached thereto and terminating in a sulfonyl group are suitable for use in the present invention.
  • Examples of such sulfonic ion exchange group fluoropolymers are illustrated, for example, in U.S. Patents 4,578,512; 4,554,112; 4,515,989; 4,478,695; 4,470,889; 4,462,877; 4,417,969; 4,358,545; 4,358,412; 4,337,211; 4,337,137; and 4,330,654.
  • the ionomer has a substantially fluorinated polymer backbone and a recurring pendent group having the formula:
  • ionomers useful in forming both thick and thin composite membrane layers are characterized by a substantially fluorinated polymer backbone and a recurring pendent group having the formula:
  • Ionomers having the above formulas are disclosed in U.S. Patents 4,478,695; 4,417,969; 4,358,545; 4,940,525; 3,282,875; and 4,329,435.
  • the ionomer is preferably present in an amount, based on the weight of the composition, of at least 0.5 percent but preferably no more than 5 percent.
  • the ionomer may be utilized in any ionic form, such as the proton form or salt form of the corresponding oligomer or polymer. Examples of salt forms include quaternary ammonium, sodium, lithium, and potassium. For most chlor-alkali applications it is preferred that the ionomer be used in the sodium salt form.
  • the ionomers used to prepare the inks preferably have an equivalent weight, based on the number of pendant ionic groups per molecule, of at least 600, more preferably at least 700, and preferably no greater than 1200, more preferably no greater than 950.
  • the ionomer must also be substantially insoluble in water at temperatures below 100°C; therefore, the minimum equivalent weight for certain fluoropolymers may be higher.
  • substantially insoluble in water means that the pure ionomer in the ionic form is at least 75 percent insoluble in distilled water at any concentration.
  • the difference between the equivalent weight of the ionomers in at least two of the inks used to prepare the MEA is preferably at least 50, more preferably at least 100, and is most preferably at least 300; but is preferably no greater than 800, more preferably no greater than 600, and is most preferably no greater than 400.
  • the ionomer used to prepare the ink preferably has an equivalent weight of at least 650, more preferably at least 700, and is most preferably at least 770; but is preferably no greater than 950, more preferably no greater than 900, and is most preferably no greater than 840.
  • the equivalent weight of the ionomer may be determined by any suitable technique, such as titration with a base, as illustrated in U.S. Patent 4,940,525.
  • a membrane (11) is shown, having two active layers positioned on the cathode side of the membrane.
  • the active layer closest to the membrane (13) contains ionomers having a different average equivalent weight than the active layer positioned adjacent thereto (15). If desired, the ionomer with the lowest average equivalent weight can be closest to the membrane.
  • the porous layer (16) is a layer of an electrically conductive porous material having at least two portions with different mean pore sizes and is located between the active layer and the flow field.
  • the flow field (17) may comprise a machined graphite plate, or may be primarily comprised of a thicker layer of porous carbon material as described, for example, in U.S. Patent 5,252,410.
  • the porous layer (16) does not contain any catalysts which are typically present in the active layer, such as platinum.
  • the electrolytic cells usefuLin the fourth and fifth aspects of the invention contain a layer of an electrically conductive porous material (hereafter, "intermediate layer") which is adjacent to the membrane electrode assembly and has at least two portions with different mean pore sizes.
  • the portion of the layer adjacent to the membrane electrode assembly (18) (hereafter, "small pore region”) has a mean pore size which is at least ten times smaller than the portion of the layer adjacent to the opposite side of the layer (19) (hereafter, "large pore region”).
  • compositions suitable for use in the preparation of the intermediate layer include any organic or inorganic composition which can be fabricated into a solid layer having the porosity and pore size characteristics referred to above, and which also has sufficient dimensional, hydrolytic and oxidative stability under the operating conditions of the electrolysis cell.
  • One method of preparing an intermediate layer having asymmetrical pore size characteristics is to prepare such a layer from two or more materials having different mean pore sizes.
  • An example of such a method is to first obtain or prepare a material having a mean pore size suitable for the large pore region (hereafter, "large pore material”), and then infiltrate and/or coat one side of the material with a composition which will reduce the porosity of a portion of the material sufficiently to obtain the smallest desired pore size, and/or form a discrete layer of the composition on the outside of the material having the desired small pore characteristics.
  • large pore material a material having a mean pore size suitable for the large pore region
  • the membrane and the layer of polymer containing a metal catalyst must be hydrated in order to be sufficiently ionically conductive.
  • water passes through the membrane and through cathode and is removed via the adjacent flow field.
  • Water vapor is also preferably present to humidify the oxygen-containing feed gas.
  • the efficiency of the electrolytic cell is reduced, since diffusion of gas through liquid water is slow relative to its diffusion through water vapor.
  • the small pore region of the layer reduces the accumulation of excess liquid water in or next to the active layer because it serves as a semi-permeable layer or membrane which permits the water vapor generated within the active layer or present due to the humidification of the reactant gases to pass between the active layer and the flow field, but reduces or prevents condensation of water on the active layer and reduces or prevents the liquid water present in the flow field or large pore region of the intermediate layer from passing back through the small pore region to the active layer.
  • the wettability (determined by the pore size and water-solid contact angle) of the small pore region is such that for a sufficiently large fraction of the pores the displacement pressure required to force liquid water into these pores is larger than the hydraulic pressure in the flow field components under the prevailing condition of pressure and temperature in the electrolytic cell.
  • suitable organic compositions which may be used to prepare or infiltrate the large pore material include thermoplastic or thermosetting polymeric and oligomeric materials, such as polytetrafluoroethylenes, including those which have sulfonic acid groups, (such as NationalTM, available from DuPont), poly(alkylene oxide)s, polyolefins, polycarbonates, benzocyclobutanes, perfluorocyclobutanes, polyvinyl alcohols, and polystyrene, epoxy resins, perfluoroalkyl/acrylic copolymers, polyanilines, polypyrroles, as well as mixtures thereof.
  • thermoplastic or thermosetting polymeric and oligomeric materials such as polytetrafluoroethylenes, including those which have sulfonic acid groups, (such as NationalTM, available from DuPont), poly(alkylene oxide)s, polyolefins, polycarbonates, benzocyclobutanes, perfluorocyclobutanes, polyvinyl alcohol
  • the composition is a polytetrafluoroethylene, perfluoroalkyl/acrylic copolymer, or a perfluorocyclobutane, and is most preferably a perfluorocyclobutane.
  • suitable inorganic compositions include silver or nickel metal, nickel oxide, and titanium-based compositions.
  • the composition used to prepare the small pore region of the intermediate layer preferably contains polymer, carbon particles, and a suitable carrier.
  • the carrier will typically infiltrate the entire large pore material, although the majority of the polymer and carbon particles will collect on or close to the surface of the side of the material to which it is applied (depending on its porosity and the size of the particles contained in the composition), thereby forming the small pore region on the side of the material to which the composition is applied.
  • the regions or portions of the intermediate layer having different mean pore sizes are not necessarily discrete layers, so long as at least the first 1 micron of depth of the small pore region and at least the first 50 microns of depth of the large pore region (as measured from the surface of the layer in a direction perpendicular to the layer) has the necessary pore characteristics.
  • the intermediate layer may also be prepared by applying the composition used in the preparation of the small pore region to the membrane electrode assembly, and then positioning or laminating a layer of a large pore material adjacent thereto.
  • a film of the composition used in the preparation of the small pore region may be prepared separately using conventional film manufacturing techniques, and then positioned or laminated between the membrane electrode assembly and the large pore material. If the composition is applied to the MEA, it may be applied using any suitable coating technique, such as by painting or silk-screening.
  • the small pore region of the intermediate layer is preferably at least as hydrophobic as the active layer.
  • the composition used to prepare the small pore region is preferably a liquid-based composition which will solidify after application. If the composition which is applied is solvent-based, enough of the solvent is removed to form a solid layer of material prior to assembling the electrolytic cell. Such solvent may be removed either at ambient conditions or at elevated temperatures. If appropriate, the composition is heated to increase its stability and uniformity, such as by crosslinking, molecular weight advancement, or agglomerating latex particles.
  • the composition used to prepare the small pore region is to be applied directly to the membrane electrode assembly, the majority of the dissolved solids contained therein (such as the polymer) are preferably hydrophilic in character, since the membrane and active layer are normally prepared from a hydrophilic composition, and application of a solution of a primarily hydrophobic dissolved solids would normally be expected to adversely affect the properties of the active layer.
  • the composition used to prepare the small pore region is still preferably hydrophobic after being cured.
  • Hydrophobic fillers such as carbon fibers and/or powders treated with hydrophobic compositions such as silane- and fluorine-based compositions, may be used in the compositions that are used to prepare the small pore region to give it some hydrophobic character and affect the wettability of its pores, as well as increase the porosity and mean pore size of the solidified composition.
  • the weight ratio of carbon fibers or powders to the other components in the composition is preferably at least 1:1, more preferably at least 3:1; and preferably no greater than 10:1, more preferably no greater than 5:1; and is most preferably 3: 1.
  • the small pore region is prepared by applying the composition to a large pore material, such as a graphite paper
  • a large pore material such as a graphite paper
  • the relatively fine pore structure of the paper will help keep the majority of fillers in the composition close to the surface on the side of the paper to which it is applied.
  • the composition may be one which is primarily hydrophilic as applied, but hydrophobic upon curing, such as a polytetrafluoroethylene latex.
  • the small pore region is prepared by applying a hydrophilic composition to a large pore material, a thin coating of a highly hydrophobic material such as ZonylTM 7040, a perfluoroalkyl acrylic copolymer available from DuPont, may be applied to the side of the small pore region facing the MEA to further increase its hydrophobicity.
  • a highly hydrophobic material such as FluoradTM FC 722 and FC 724, available from 3M.
  • the MEA suitable for use in the fourth and fifth aspects of the invention are preferably prepared by applying the catalyst ink (a suspension or dispersion of the catalyst) directly to the membrane as described, for example, in U.S. Patent 5,211,984.
  • the catalyst ink a suspension or dispersion of the catalyst
  • the composition used to prepare the small pore region is preferably applied first, followed by the catalyst ink, so that the infiltrated porous carbon material may be utilized as an intermediate layer, as well as a support layer for the catalyst.
  • this method, as well as any methods which require the preparation of a separate film for the intermediate layer are less preferred since such films and catalyst- containing structures must typically be laminated to the membrane portion of the membrane electrode assembly in order to assemble the electrolytic cell.
  • Such lamination processes, wherein heat and/or excessive pressure is applied to the intermediate layer may alter or damage its pore structure.
  • the composition of the intermediate layer may be formulated to minimize the voltage at which the electrolytic cell will operate at a given current density. It is believed that lower cell voltages at higher current density require the small pore region to be more hydrophobic than at lower current densities. For example, if a lower cell voltage at a lower current density is desired, compositions having a higher carbon/polymer ratio (such as 5:1) are preferred for use in the preparation of the small pore region, particularly when applied to a graphite paper having a relatively low porosity. Likewise, if lower cell voltages at higher current densities are preferred, lower carbon/polymer ratios (such as 3:1) are preferred, particularly when applied to a graphite paper having a relatively high porosity.
  • the small pore region preferably has a thickness in the range of from 1 micron to 150 microns (as measured in a direction perpendicular to the intermediate layer), and has the desired porosity and pore size characteristics. More preferably, the region has a thickness in the range of from 5 to 25 microns.
  • the portion of the region adjacent to the MEA is sufficiently porous to permit the transmission of water vapor through the region.
  • the porosity of this portion of the region is preferably at least 10 percent.
  • the mean pore size of the small pore region is preferably at least 0.1 micron, more preferably at least 1 micron; but is preferably no greater than 10 microns.
  • the mean pore size may be measured by any convenient method, such as by mercury porosimetry.
  • the device used to measure the mean pore size distribution of the layer may be calibrated using silica/alumina calibration standards (available from Micrometrics, Norcross, GA).
  • the porosity of the small pore region is preferably at least 10 percent.
  • Conductive fillers and non-conductive inert or fugitive fillers may be incorporated into the composition to achieve the desired pore structure.
  • Intrinsically conductive polymers such as doped polyaniline or polypyrrole may also be used to prepare the composition in order to increase its conductivity.
  • the pore structure of the small pore region may also be controlled to some extent by the selection of the polymer or the use of an oligomeric composition.
  • the large pore region preferably has a thickness of at least 2 mils (0.05 mm), more preferably at least 6 mils (0.15 mm); but is preferably no greater than 50 mils (1.27 mm).
  • the porosity of this region is preferably at least 82 percent, more preferably at least 85 percent, and most preferably at least 87.5 percent.
  • the mean pore size of the large pore region is preferably at least 30 microns. The porosity and pore size values given above represent the characteristics of the small pore region for at least the first micron of its depth from the side of the intermediate layer next to the MEA and at least the first 50 microns of its depth from the opposite side of the intermediate layer, regardless of its method of preparation.
  • the porous carbon material may be treated with a perfluorosilane or fluorine composition to increase its hydrophobicity, or oxidized, sulfonated, or coated with a hydrophilic material to increase its hydrophilicity. If a porous carbon material is utilized as both the flow field and the large pore material may have interdigitated channels cut into it to lower the pressure drop introduced into the oxygen-containing feed gas.
  • the conductivity of the intermediate layer is preferably at least 0.01 Siemens/cm (S/cm), more preferably at least 0.1 S/cm, and most preferably at least 10 S/cm.
  • the conductivity of the layer may be increased by the addition of conductive fillers, such as carbon fibers or particles, or by the incorporation of conductive salts or polymers.
  • conductive fillers such as carbon fibers or particles
  • conductive salts or polymers such as carbon fibers or particles
  • Alternatives to the above porous carbon materials which may be advantageously used as the large pore material include fine mesh woven wire screens and expanded metal, or porous metals, especially those made from silver or nickel.
  • a particularly well-suited form of catalyst ink comprises a) catalytically-active particles; b) an organic compound having a pKa of at least 18 and a basicity parameter ⁇ , of less than 0.66 and c) a polymeric binder.
  • a layer of this composition can be applied to a solid polymer electrolyte, a carbon fiber paper, or a release substrate, then heated under conditions sufficient to volatize at least 95 percent of the organic compound. The resulting composition can then be placed in contact with the solid polymer electrolyte (if the composition was not directly applied to the solid polymerelectrolyte initially).
  • this catalyst ink when used to prepare a membrane electrode assembly (MEA) having a solid polymer electrolyte, provides an MEA which provides a relatively low cell voltage at a given current density and gas flow rate in a electrolytic cell. It is believed, without intending to be bound by any particular theory, that the improved performance results from the ability of the organic compound to be easily volatized when heated, which is believed to result from a low incidence of ionic, hydrogen, or covalent bonds or partial bonds formed between the organic compound and the polymeric binder, particularly when the binder is in an ionic form.
  • the characteristics of the organic compound set forth in the above summary are measurable characteristics which are believed to be indicative of a compound with a minimal or nonexistent propensity to bond with an ionomer or polar polymer.
  • the pKa and basicity parameter reflect the acidity and basicity of the compound, respectively.
  • the ease with which the organic compound may be removed from the ink significantly affects the pore characteristics of the resulting active layer.
  • Easy removal of the organic compound is believed to promote a "foaming" effect in the layer, which increases the porosity of the pores of the layer.
  • the pore characteristics affect the transport of water though the layer, which significantly affects the performance of the MEA into which it is incorporated.
  • the composition of the seventh aspect of the invention hereafter, "catalyst ink”
  • the composition of the invention permits the use of Na-f- or H+ forms of ionomers as the binder without significant degradation thereof when the catalyst ink is heated to volatilize the organic compound, and provides an active layer with good long-term stability.
  • Suitable organic compounds include organic compounds having a pKa (the negative logarithm (to the base 10) of the equilibrium constant, K, for the reaction between the compound and water) of at least 18 and a basicity parameter, ⁇ , of less than 0.66.
  • the pKa is at least 25.
  • ⁇ is less than 0.48, and is more preferably less than 0.40.
  • the basicity parameter for a number of organic compounds, as well as reference procedures for its determination, are described in Kamlet et al., "Linear Solvation Energy Relationships. 23. A Comprehensive Collection of the Solvochromatic Parameters, ⁇ *, oc, and ⁇ , and Some Methods for Simplifying the Generalized Solvatochromic Equation," J. Org. Chem., Vol. 48, pp. 2877-2887 (1983).
  • the compound volatilizes at temperatures in the range of from 100°C to 250°C without significant degradation which can impair the performance of the active layer.
  • a relatively low volatilization temperature is also preferred, since organic compounds (component (b)) that are not removed from the layer can add to the electrical resistance of the layer, causing poorer MEA performance.
  • This characteristic is particularly important when the binder is utilized in its proton form, since the binder will act as a catalyst to further promote the degradation of any residual organic compound.
  • the use of a proton form of the binder has advantages, however, since quaternary ammonium cations present in an ink composition are difficult to remove and may contribute to a long "break in" period when an electrolytic cell or electrolytic cell stack is initially started.
  • the boiling point of the solvent is greater than 100°C so that, upon curing of the ink, the water or low boiling solvents which may be present in the ink (typically introduced to the ink by way of a commercially available binder containing such components) are removed first.
  • suitable organic compounds for use as component (b) include ethylene carbonate, propylene carbonate, butylene carbonate, ethylene carbamate, propylene carbamate, and butylene carbamate, acetone, acetonitrile, difluorobenzene, and sulfolane, but is most preferably propylene carbonate.
  • the organic compound is preferably present in an amount, based on the weight of the composition, of at least 10 percent, more preferably at least 20 percent, and is most preferably at least 30 percent; but is preferably no greater than 90 percent.
  • Suitable polymeric binders for use in the preparation of this preferred catalyst ink include any polymer or oligomer having ionic conductivity of at least lxlO "3 S/cm, more preferably at least 10 " S/cm (under the operating conditions of the electrolytic cell) or electrolytic cell, or which may be reacted with acid or base to generate an oligomer or polymer having ionic conductivity.
  • the binder has pendant ionic groups, it preferably has an equivalent weight of at least 600, more preferably at least 700, and preferably no greater than 1200, more preferably no greater than 950.
  • the equivalent weight of the binder is based on the number of pendant ionic groups per molecule, as may be determined by any suitable technique, such as titration with a base, as illustrated in U.S. Patent 4,940,525.
  • suitable binders include perfluorinated polymers and polytetrafluoroethylene polymers, and polytetrafluoroethylene polymers having pendant sulfonic acid groups, (such as NationalTM, available from DuPont).
  • the binder is preferably present in an amount, based on the weight of the composition, of at least 0.5 percent but preferably no more than 5 percent.
  • the ionomer may be utilized in any ionic form, such as the proton form or salt form of the oligomer or polymer. Examples of salt forms include quaternary ammonium, sodium, lithium, and potassium.
  • Another method for preparing an MEA useful in the present invention comprises applying one or more layers of the catalyst ink to a release material, such as a polytetrafluoroethylene-coated substrate, curing the ink, and then laminating the cured material to the membrane.
  • a third method comprises applying one or more layers of the catalyst ink to one side of a sheet of porous carbon material, such as a carbon or graphite paper, and then placing the side of the material to which the ink was applied adjacent to the membrane. If the ink is cured before being placed next to the membrane, it should then preferably be laminated to the membrane to ensure good contact between the two.
  • the ink may be cured using any suitable method for removing at least 95 percent of component (b), as well as any other volatile organic solvents contained in the ink, such as by heating at an elevated temperature optionally under reduced pressure.
  • the ink is heated to a temperature at which the component (b) is volatile, but below its boiling point.
  • the inks preferably contain a polytetrafluoroethylene polymer having pendant sulfonic acid groups as the binder, and the layer of ink closest to the membrane has an equivalent weight which differs from the equivalent weight of the binder in the ink layer adjacent thereto by at least 50.
  • the ink is heated under conditions sufficient to remove at least 99 percent, more preferably at least 99.9 percent of component (b).
  • the ink is applied in an amount sufficient to provide a layer of the composition which, when dry and protonated, has a thickness of at least 1 ⁇ m, more preferably at least 5 ⁇ m, and most preferably at least 10 ⁇ m; but is preferably no greater than 30 ⁇ m.
  • the porosity of the layer is preferably at least 30 percent, more preferably at least 50 percent; but is preferably no greater than 90 percent, more preferably no greater than 60 percent.
  • the mean pore size of the layer is preferably at least 0.01 ⁇ m, more preferably at least 0.03 ⁇ m; but is preferably no greater than 10 ⁇ m, more preferably no greater than 0.5 ⁇ m, and is most preferably 0.1 ⁇ m.
  • the coating on the release substrate was then pressed into a perfluorinated cation exchange membrane (obtained from DuPont under the trade name Nafion 115) which had been converted to the sodium form by soaking in 0.5M NaOH for 30 minutes, rinsed in deionized water and vacuum dried for 30 minutes at 55°C.
  • the resulting catalyst layer was 5-10 microns thick.
  • the Teflon release substrate was removed, leaving the membrane with the active layer coated onto it.
  • Carbon paper was made hydrophobic by submerging it into 5-10 percent solution of perfluorocyclobutene (PFCB) in mestylene.
  • the paper was vacuum dried at 200°C for at least an hour. The edges of the paper were then sealed with epoxy requiring a room temperature cure overnight.
  • the carbon paper was held rigidly in place between the catalyst layer side of the MEA and a Lexan support block in an electrolysis cell.
  • 5N NaOH was used as the anolyte in place of the brine of a normal chlor-alkali cell. In this situation the anodic product is oxygen rather than the chlorine of a brine cell.
  • the membrane side of the MEA faced an aperture where 5N NaOH was introduced.
  • a stainless steel anode was at the far end of the aperture.
  • the NaOH solution was circulated through the aperture by pumping from a reservoir.
  • a silver- silver chloride reference electrode in the reservoir was used to measure the cathode potential.
  • the NaOH solution was heated to 55°C.
  • Oxygen was bubbled through 80°C water at 5 psig (34.5 kPa) and introduced to the cathode through the carbon paper.
  • the gas is delivered to one edge of the carbon paper via a slot in the Lexan support block, forced to travel in the plane of the carbon paper and collected at the opposite edge exiting through a second slot in the Lexan block. Current is passed between the anode and the cathode.
  • the cathode potential is recorded at various current densities, and was compared to when nitrogen was introduced in the same circumstances in the identical system. As seen from Figure 5, the comparison showed that the potential when oxygen was fed to the electrode was 0.77 to 0.90 volts less than when nitrogen was fed to the electrode.
  • the cathode and cell are made as in example 1 except the carbon paper flow field was made hydrophilic by placing it in a solution consisting of 0.5 g Ag 2 SO ,15g Na 2 S 2 O 8 and 300 ml of concentrated H 2 SO for 1 hour at 70°C.
  • the difference in cathode polarization between oxygen and nitrogen feed is shown in Figure 6.
  • the depolarization varies between 0.27 and 0.61V between 0.25 and 2.25 A/in 2 (0.039 and 0.35 A/cm 2 ).

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Abstract

L'invention porte sur un procédé d'électrolyse d'une saumure d'halogénures de métaux alcalins effectué dans une cellule électrolytique pourvue d'un compartiment anodique possédant au moins une anode, un compartiment cathodique possédant au moins une cathode, et une membrane en contact avec la cathode (formant un ensemble d'électrodes à membranes) qui sépare le compartiment anodique du compartiment cathodique. Ce procédé consiste (a) à introduire la saumure d'halogénures de métaux alcalins dans le compartiment anodique; (b) électrolyser cette saumure pour produire un gaz halogène et des ions de métaux alcalins; (c) faire passer les ions de métaux alcalins et l'eau par la membrane pour les amener dans le compartiment cathodique; et (d) introduire un gaz contenant de l'oxygène dans le compartiment cathodique de façon à réduire l'oxygène à la cathode et produire une solution concentrée d'hydroxyde de métaux alcalins. Ce procédé est également caractérisé par une zone d'écoulement qui est placé à côté de la cathode de façon à faciliter le transport du gaz oxygène vers la cathode et retirer de cette dernière l'hydroxyde de métaux alcalins, la zone d'écoulement comprenant un matériau électroconducteur dont la porosité est d'au moins 30 % et sa granulométrie moyenne d'au moins 10 microns.
PCT/US1998/006769 1997-04-07 1998-04-03 Electrolyse de saumures d'halogenures de metaux alcalins effectuee au moyen de systemes cathodiques comprenant de l'oxygene WO1998045503A1 (fr)

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EP98914515A EP0979318A1 (fr) 1997-04-07 1998-04-03 Electrolyse de saumures d'halogenures de metaux alcalins effectuee au moyen de systemes cathodiques comprenant de l'oxygene
AU68854/98A AU727997B2 (en) 1997-04-07 1998-04-03 Electrolysis of alkali metal halide brines using oxygen cathode systems
CA002286175A CA2286175A1 (fr) 1997-04-07 1998-04-03 Electrolyse de saumures d'halogenures de metaux alcalins effectuee au moyen de systemes cathodiques comprenant de l'oxygene

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WO2007116095A2 (fr) * 2006-04-12 2007-10-18 Industrie De Nora S.P.A. Electrode de diffusion gazeuse pour cellules a percolation electrolytique
WO2008067411A2 (fr) * 2006-11-28 2008-06-05 Miox Corporation Générateur sur site à faible maintenance
US8455010B1 (en) 2007-10-31 2013-06-04 Reoxcyn Discoveries Group, Inc Product and method for producing an immune system supplement and performance enhancer
WO2013086470A3 (fr) * 2011-12-08 2015-06-18 Allan Riggs Appareil formant batterie auto rechargeable, et procédé pour son fonctionnement
US9255336B2 (en) 2007-10-31 2016-02-09 Reoxcyn Discoveries Group, Inc. Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic
US10400349B2 (en) 2006-11-28 2019-09-03 De Nora Holdings Us, Inc. Electrolytic on-site generator

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US7048842B2 (en) * 2001-06-22 2006-05-23 The Procter & Gamble Company Electrolysis cell for generating chlorine dioxide
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GB2385602B (en) * 2002-02-20 2004-04-21 Itm Power Ltd Method of photoelectrolysis
US7318888B2 (en) 2002-02-20 2008-01-15 Itm Power Ltd Method of photoelectrolysis
GB2385602A (en) * 2002-02-20 2003-08-27 Itm Power Ltd Photoelectrolysis
TWI419398B (zh) * 2006-04-12 2013-12-11 Industrie De Nora Spa 電化電池用之氣體擴散電極及其製法
WO2007116095A2 (fr) * 2006-04-12 2007-10-18 Industrie De Nora S.P.A. Electrode de diffusion gazeuse pour cellules a percolation electrolytique
WO2007116095A3 (fr) * 2006-04-12 2008-01-24 Industrie De Nora Spa Electrode de diffusion gazeuse pour cellules a percolation electrolytique
NO345401B1 (no) * 2006-04-12 2021-01-18 Industrie De Nora Spa Elektrokjemisk elektrolyttperkoleringscelle, samt fremgangsmåte og anvendelse derav
JP2009533553A (ja) * 2006-04-12 2009-09-17 インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ 電解液浸透型セル用ガス拡散電極
AU2007235879B2 (en) * 2006-04-12 2010-07-22 Industrie De Nora S.P.A. Gas-diffusion electrode for electrolyte-percolating cells
KR101365955B1 (ko) 2006-04-12 2014-02-21 인두스트리에 데 노라 에스.피.에이. 전해질-침투 전지용 가스-확산 전극
US7972484B2 (en) 2006-04-12 2011-07-05 Industrie De Nora S.P.A. Gas diffusion electrode for electrolyte-percolating cells
WO2008067411A2 (fr) * 2006-11-28 2008-06-05 Miox Corporation Générateur sur site à faible maintenance
US7922890B2 (en) 2006-11-28 2011-04-12 Miox Corporation Low maintenance on-site generator
US10400349B2 (en) 2006-11-28 2019-09-03 De Nora Holdings Us, Inc. Electrolytic on-site generator
WO2008067411A3 (fr) * 2006-11-28 2008-07-17 Miox Corp Générateur sur site à faible maintenance
US11421337B2 (en) 2006-11-28 2022-08-23 De Nora Holdings Us, Inc. Electrolytic on-site generator
US8455010B1 (en) 2007-10-31 2013-06-04 Reoxcyn Discoveries Group, Inc Product and method for producing an immune system supplement and performance enhancer
US9255336B2 (en) 2007-10-31 2016-02-09 Reoxcyn Discoveries Group, Inc. Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic
WO2013086470A3 (fr) * 2011-12-08 2015-06-18 Allan Riggs Appareil formant batterie auto rechargeable, et procédé pour son fonctionnement
US9455482B2 (en) 2011-12-08 2016-09-27 Argopower, Llc Self-recharging battery apparatus and method of operation

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