WO1988006643A1 - Membranes ionomeres pour electrodes a diffusion gazeuse supportant la pression - Google Patents

Membranes ionomeres pour electrodes a diffusion gazeuse supportant la pression Download PDF

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Publication number
WO1988006643A1
WO1988006643A1 PCT/US1988/000622 US8800622W WO8806643A1 WO 1988006643 A1 WO1988006643 A1 WO 1988006643A1 US 8800622 W US8800622 W US 8800622W WO 8806643 A1 WO8806643 A1 WO 8806643A1
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WIPO (PCT)
Prior art keywords
gas
electrode
cell
electrolyte
contacting surface
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Ceased
Application number
PCT/US1988/000622
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English (en)
Inventor
Arnold Z. Gordon
Ernest B. Yeager
Donald S. Tryk
M. Sohrab Hossain
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Gould Inc
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Gould Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes

Definitions

  • This invention relates generally to gas diffusion electrodes and, more particularly, this invention relates to gas diffusion electrodes adapted for use in electrochemical cells utilizing an aqueous alkaline electrolyte and consuming or generating a gas via the electrochemical process occurring within the gas diffusion electr ⁇ de.
  • gas diffusion electrodes have also been used in the electrolysis, either oxidation or reduction, of gaseous reactants. It is also possible to generate gases in such electrodes.
  • gas diffusion electrodes take the form of solid porous (gas and liquid pemeable) bodies formed at least in part of an electronically conductive, electrochemically active material, and may include a catalyst. Such electrodes generally define an electrolyte contacting surface and a gas contacting surface. Electrochemical oxidation and reduction occur at the points in the electrode where the gas to be oxidized or reduced contacts both the electrolyte and the active material of the electrode. In the case of gas generation, electrolyte contacts the active material and gas is generated at this interface.
  • Electrochemical cells utilizing such electrodes generally comprise the gas diffusion electrode, a spaced counter electrode, a liquid electrolyte (which is generally aqueous) which contacts
  • Electrochemical batteries for example, the metal-air type, commonly utilize either an aqueous
  • alkaline or neutral (e.g., saline) electrolyte While fuel cells may commonly utilize either acidic electrolytes or alkaline electrolytes. Other types of electrolytes are also used, depending upon the specific gas which is consumed or generated.
  • the present invention is generally applicable to all such types of gas diffusion electrodes and cells.
  • the electronically conductive material in a gas diffusion electrode typically may be carbon.
  • catalysts such as platinum or transistion metal organometallic catalysts (such as prophyrins) are available.
  • SUBSTITUTE SHEET and/or flowed gaseous reactant are of course accompanied by a pressure drop across the cell, especially on the electrolyte side. This can be lead to excess pressures either on the gas-side or the electrolyte-side of the electrode. Furthermore, it may be desirable in certain circumstances to operate at an elevated gas pressure with respect to the electrolyte pressure. One example of such a situation would be one in which the performance is increased by pressurizing the gaseous reactant. In battery and fuel cell applications, it is desirable to obtain as high a cell voltage as possible at any given current density. One means of accomplishing this is to utilize a relatively high gas pressure or flow rate. The use of a porous (e.g.
  • blow-through pressure typically 30-60% porosity gas diffusion electrode
  • gas pressure exceeds liquid electrolyte pressure by a sufficient amount, "blow-through" of gas through the electro ' de into the liquid electrolyte results.
  • this so-called “blow-through pressure” is usually much lower than is desirable for tolerance of substantial differential pressures between the gas and liquid sides of the cell.
  • typical air cathodes exhibit a gas blow-through pressure of less than about 0.25 psi. If the differential pressure exceeds the blow-through pressure, pumping of gas into the liquid electrolyte may result.
  • typical blow-through pressures range from 0-1 psi, and are determined primarily by interfacial tension and pore size distribution.
  • liquid electrolyte pressure is higher than the gas pressure and the differential pressure exceeds the liquid bleed-through pressure
  • SUBSTITUTESHEET liquid may be pumped into the gas side of the cell, which may result in liquid in the gas manifold, with consequent pumping problems and a decrease in cell performance and useful cell life due to flooding of the active layer of the electrode.
  • gas-generating cells it is customary for the gas to be generated on the front face (electrolyte- side) of the electrode.
  • the gas is thus generated as bubbles in the electrolyte, which can lead to removal of electrolyte from the cell and increased oh ic losses.
  • Generation of gas in a gas diffusion electrode is more desirable because the gas can exit the cell directly through the back of the electrode. Operation in this mode would require a certain amount of pressure tolerance. Even higher pressure tolerance would be required if the gas is generated in a pressurized state.
  • SUBSTITUTESHEET voltage loss across the electrode A voltage loss of less than 0.05 volts is preferred with voltage losses of up to 0.25 volts being generally acceptable.
  • an ionomeric, ionically conductive, substantially gas impermeable membrane is disposed over substantially the entire electrolyte contacting surface of a gas diffusion electrode adapted for use in a gas generating or consuming electrochemical cell utilizing an aqueous alkaline liquid electrolyte.
  • the membrane comprises a hydrophilic anion exchange resin, and is applied directly on the electrolyte contacting surface in a preformed state.
  • the invention also comprehends an electrochemical cell comprising the coated gas diffusion electrode spaced from a counter electrode and in contact with an aqueous alkaline liquid electrolyte.
  • a gas to be oxidized, reduced or generated is in contact with the gas side of the electrode, and circuit connections are disposed between the counter and gas diffusion ' electrodes.
  • the electrode and cell of the invention are capable of operating at very high gas vs. electrolyte differential pressures at high current densities without significant voltage loss.
  • Fig. 1 is a transverse sectional view of one embodiment of an electrochemical cell in which the invention may be utilized;
  • Fig. 2 is a schematic sectional view of a typical gas diffusion electrode with which the invention may be utilized;
  • Fig. 3 is a sectional view of an electrode holder useful in testing gas diffusion electrodes
  • Fig. 4 is a schematic exploded perspective view of an electrode assembly adapted for use with the electrode holder of Fig. 3;
  • Fig. 5 is a schematic transverse sectional view of a gas diffusion electrode useful in the embodiments of Figs. 3 and 4;
  • Fig. 6 is a series of polarization curves exhibited by an electrode made according to. the invention
  • Fig. 7 is a series of polarization curves exhibited by another embodiment of an electrode made according to the invention.
  • Fig. 8 is a plot of potential vs. time for oxygen reduction carried out with the electrode of Fig. 7;
  • Fig. 9 is a series of polarization curves for another embodiment of the invention at varying temperatures at a differential pressure of 1 psi (6.9 kPa) .
  • Fig. 1 illustrates a typical embodiment of an electrochemical battery utilizing a gas diffusion electrode.
  • This particular cell is an aqueous alkaline lithium-air cell. It is to be understood that the present invention is not limited to use in ' electrochemical batteries, nor to cells in which gas is consumed. Rather, the invention finds wide applicability in cells in which gas is either consumed or produced, via either reduction or oxidation, in which any of various electrolytes are used, etc.
  • an electrochemical cell in Fig. 1, includes an anode 11, a gas consuming cathode 12, and a metal screen 13 interposed between the anode 11 and cathode 12 within an outer housing 14.
  • the screen 13 is in electrical contact with the cathode 12, and is in mechanical (but not electrical) contact with the anode 11.
  • the anode 11 comprises a lithium anode, which may comprise elemental lithium metal or lithium alloyed with alloying material such as small amounts of aluminum.
  • the screen 13 is not in electrical contact with the anode 11, due to the presence of an insulting, porous lithium hydroxide (LiOH) film which is formed on the anode surface by contact thereof w .th humid air, and is well known in the art. It is to be noted, however, that this particular feature is peculiar to the aqueous lithium-air cell. In other types of metal-air batteries and fuel cells, either an electrically insulating porous separator layer or a simple electrolyte gas would be used. It should also be noted that the screen 13 is
  • SUBSTITUTE SHEET necessary to help restrain the gas diffusion electrode 12 against the gas pressure.
  • the cathode 12 is in this case an air cathode through which atmospheric air flows. Those skilled in the art, however, will recognize that such a cathode may operate with any oxygen-containing gas.
  • One surface 15 of the cathode 12 is exposed to ambient atmosphere (or a source of another oxygen- containing gas) in a chamber 16 of the housing 14, and the opposite surface 17 of the cathode 12 is contacted by the liquid electrolyte 18 which is flowed through a second chamber 19 in the housing 14 as by a suitable pump 20.
  • the electrolyte is provided from a reservoir 21 for suitable delivery when needed.
  • the anode 11 and cathode 12 each terminate in a respective terminal 26 or 28, and are connected to a load 30 through suitable circuit connections 32.
  • the cathode 12 comprises a structure formed of a suitable porous hydrophobic material, such as polytetrafluoroethylene (PTFE), mixed with carbon black, both pure and catalyst-containing.
  • PTFE polytetrafluoroethylene
  • the screen 13 illustratively may comprise a woven metal wire screen formed of suitable non-corroding metal, which in the case of alkaline electrolyte may be nickel or silver plated nickel. If desired, the screen 13 may serve" as a current collector if connected to the terminal 28.
  • liquid electrolyte in this case an aqueous alkaline electrolyte such as aqueous lithium hydroxide, is flowed through the chamber 19 by means of the pump 20. As such, there is a pressure drop across the chamber 19 in the direction of flow.
  • aqueous alkaline electrolyte such as aqueous lithium hydroxide
  • Fig. 1 is intended to be exemplary only, as the invention is applicable to any of a variety of types of gas diffusion electrodes and electrochemical cells.
  • Fig. 2 is a schematic depiction of the structure of a preferred embodiment of the cathode 12.
  • the electrode 12 is formed essentially of a two or three component laminate defining the gas contacting surface 15 and the opposed electrolyte contacting surface 17.
  • An electronically conductive porous gas carrier layer 40 defines the gas contacting surface 15 and typically is a mixture of a hydrophobic material such as porous PTFE (e.g. Teflon brand PTFE) with a carbon black such as Shawinigan black (Chevron Chemical Co., Olefins and Derivatives Div., Houston, TX) .
  • a hydrophobic material such as porous PTFE (e.g. Teflon brand PTFE) with a carbon black such as Shawinigan black (Chevron Chemical Co., Olefins and Derivatives Div., Houston, TX) .
  • a so-called "active layer” 42 comprises a layer 44 which comprises a mixture of carbon black, or catalyst supported on carbon black, and PTFE.
  • An optional layer 46 of catalyst is disposed on the layer 44 at an interface 50.
  • layers 44 and 46 appear to be discrete layers, but in practice may define a single layer or two layers, since the catalyst is genera l ly adsorbed onto the surface of the material of layer 44. In some cases, the materials of the three layers 40, 44 and 46 may be intermixed in a single layer.
  • the entire structure of the electrode 12 of Fig. 2 is porous, generally exhibiting a porosity of 30- 60%.
  • a typical catalyst forming the layer 44 is heat-treated cobalt tetramethoxyphenyl porphyrin (CoTMPP) on a carbon black such as Vulcan XC-72 (Cabot Corp., Billerica, MA).
  • the heat treatment is typically done at 400-1000°C in inert gas.
  • the material is a currently preferred catalytic material.
  • Other catalysts include platinum,
  • the function of the layer 40 is to allow ready transmission of gas to the active layer 44. Its hydrophobicity also acts to repel liquid electrolyte which exists in the active layer 44 in order to avoid
  • Fig. 3 illustrates an electrode holder useful in measuring characteristics of gas consuming or generating electrodes.
  • the electrode holder generally designated 60, comprises a solid body 62 of a
  • SUBSTITUTESHEET communicates with a gas outlet passage 68.
  • a typical material of construction for the body 62 is 3M's Kel-F brand chloro fluorocarbon polymer.
  • An annular electrode seat 70 is defined in the body 62 in order to position an electrode assembly (not shown in Fig. 3) which includes a gas diffusion electrode, generally designated 72, adjacent the cell chamber 66.
  • a conductive (e.g. platinum) wire 74 contacts the seat 70 and extends therefrom through the outlet passage 68.
  • a threaded plug 76 of the same material as the body 62 retains an electrode assembly 80 (shown in Fig. 4) in place in the body 62.
  • Fig. 4 illustrates the electrode assembly, generally designated 80, which includes the gas diffusion electrode 72 of Fig. 3.
  • the electrode 72 is shown in schematic form in Fig. 4 and formed as cylindrical disk defining gas and electrolyte contacting surfaces 82 and 84 respectively. These surfaces are analogous to surface 15 and 17 of Fig. 1.
  • An annular conductive metal (e.g. platinum) ring 86 is disposed on the gas surface 82 between the gas surface 82 and an annular rubber gasket 88.
  • a similar rubber gasket 90 is disposed on the electrolyte side of the electrode 72 between the electrolyte contacting surface 84 and an annular ring 92 of the same material as the body 62.
  • Figs. 3 and 4 is schematic and these figures do not illustrate certain components such as the hydrophobic backing layer and associated screens.
  • Fig. 5 illustrates an exploded sectional schematic view of a typical embodiment of the diffusion electrode 72.
  • SUBSTITUTE SHEET conductive hydrophobic backing layer 102 typically of Telfon brand PTFE plus carbon black, which defines the surface 82.
  • An active layer 104 which may include a catalyst on carbon black, is adjacent to the layer 102 and defines the surface 84.
  • a membrane 106 is applied to the surface 84 and is in contact with a steel reinforcement screen 108. The membrane 106 is described in detail below.
  • the screen 100 When constructed, the screen 100 is not in physical or electrical contact with the ring 86 and thus merely acts as a physical restraint.
  • the gas inlet passage 64 and gas outlet passage 68 are connected with gas flow regulating means (not shown) which regulate the flow of gas through the passages 64 and 68 and the cell chamber 66, and thus the gas pressure in the chamber 66.
  • the screens 100 and 108 may be imbedded in the layers 102 or 106, respectively, and that the layers 102 and 104 may form a single homogeneous layer if desired.
  • the electrode 72 is in place in the assembly 80 in the electrode holder 60, a central circular segment of each of the electrode sources, respectively.
  • the electrode holder body 62 is positioned in a test cell such that the electrode surface 84 is exposed to a flowing or non-flowing (e.g. stirred) electrolyte. The remainder of the cell and associated temperature control means, etc. are omitted for clarity.
  • the steel ' screen 108 acts as a reinforcement to prevent physical rupture of the electrode 72. Flow-through of gas from the cell chamber 66 through the electrode 72 into the electrolyte side of the cell is prevented by the membrane 106 as described below.
  • the membrane 106 is a preformed membrane which is applied directly to the active layer surface 84 of the electrode preferably without adhesives or other intervening layers.
  • the membrane is of an ionomeric anionic exchange resin which is substantially impermeable to the gross passage of gas.
  • the material is an anion exchange resin and thus conducts hydroxide (OH) ions as well as water. It is also possible for bulk electrolyte to slowly diffuse through the membrane.
  • the electrode 72 may thus be effectively wetted through the membrane 106, while the membrane 106 is virtually impermeable to gas flow.
  • the membrane 106 is ionomeric, and is quite hydrophilic and readily contains and transfers ionic charge, thus allowing for minimal excess voltage loss relative to conventional gas diffusion electrodes.
  • RAIPORE R-1035 anion exchange membrane is a quaternized vinylbenzylamine grafted polytetrafluoralethylene film available in 1 mil (0.025 mm) thickness.
  • RAIPORE R-4035 anion exchange membrane is a quaternized vinylbenzylamine graft on a 2 mil (0.051 mm) preformed fluorinated polymer film.
  • RAIPORE R-5035 (L or H) anion exchange membrane is a quaternized vinylbenzylamine grafted, polyethylene exchange membrane available in 8 mil thickness. This material is available in low or high electrolytic resistances.
  • IONAC MA 3475 anion exchange membrane comprises a quaternized tetraalkyl ammonium polymer and is 16 mils (0.41 mm) thick.
  • a currently preferred anion exchange membrane is the caustic-resistant membrane (AR 108-401) from Ionics, Inc. of Watertown, Massachusetts. This material also comprises a quaternized (tetraalkyl) ammonium polymer and is approximately 1.0 mm (about 40 mils) thick.
  • useful membrane materials are characterized as being hydrophilic anionic exchange resins and these are understood by the art to contain cationic functional groups.
  • the membrane may be applied to the electrode active layer surface by mere application of pressure.
  • CoTMPP Cobalt tetramethoxyphenyl porphy in
  • CoTMPP in acetone for at least 24 hours.
  • the amount of the adsorbed macrocycle was calculated spectrophotometrically be determining its loss from the filtered solution.
  • the solid catalyst/carbon was air- dried and then heat-treated to 450°C in a horizontal tube furnace under continuous flow of purified argon.
  • Porous gas-fed electrodes were fabricated as follows: dilute (-2 mg/mL) Teflon T30 B aqueous suspension (Du Pont) was slowly added to an aqueous suspension of the catalyst/carbon while the latter was ultrasonically agitated. The mixed suspension was then filtered with a l ⁇ m pore size polycarbonate filter membrane. The paste was shaped into a 1.75 cm diameter disk in a stainless steel die using hand pressure. This disk was then applied to another disk, -0.5 mm thick, of Teflon-carbon black hydrophobic porous sheet material (Eltech Systems Corp., Fairport Harbor, OH) which contained a silver-plated Ni mesh. This dual layer disk was pressed at ' 380 kg. cm at room temperature and then heat-treated at 290°C for 2 hours in flowing helium.
  • the gas-fed electrode was placed in a Teflon- Kel-F electrode holder as shown in Fig. 3.
  • the gas (0 2 or air) pressure was applied to the back-side (hydrophobic layer) of the electrode and was monitored at the outlet.
  • a needle valve at the outlet was used to regulate the gas pressure.
  • Fig. 6 depicts a polarization curve for oxygen reduction at one atmosphere pressure (i.e. substantially zero pressure differential between gas and electrolyte sides of the electrode) with a one mm thick layer of Ionics, Inc. anion exchange membrane applied to the electrolyte side of the electrode with a stainless steel screen applied over the membrane.
  • the curves depict operation using both air and pure oxygen with the electrodes in a fully broken-in state at a temperature of 80-83°C.
  • Fig. 6 demonstrates that a current density of 100 mA/cm 2 , a potential of approximately -0.116 V was • obtained using oxygen. The is good performance, the potential being approximately 45 mV more negative than that obtained for an electrode without the membrane.
  • Fig. 7 illustrates the results of oxygen reduction tests using air or oxygen (Run 1 and 2) and oxygen after the electrode had been fully broken-in for 18 hours at a current density of 100 mA/cm (Run 3), all at a differential gas to electrolyte pressure of 1 psi. This represent a twofold increase in overpressure
  • Fig. 8 depicts the variation of potential with time for oxygen reduction carried out with the electrode of Figs. 6 and 7 at a gas/electrolyte differential pressure of 1 psi at a constant current density of 100 mA/cm 2 at 80-83°C.
  • the polarization curves of Fig. 9 depict the temperature effect on oxygen reduction polarization curves for the electrode of Figs. 6 through 8 operated at 1 psi gas/electrolyte differential pressure.
  • Another advantage of the invention is the fact that the polymer membrane stabilizes catalysts absorbed in the electrode by preventing or inhibiting dissolving of the catalysts in the electrolyte, thus preventing degradation of performance over time due to catalyst

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inert Electrodes (AREA)

Abstract

Electrodes (12) à diffusion gazeuse et cellules électrochimiques consommant ou générant du gaz (10) utilisant lesdites électrodes. L'électrode (12) se compose d'un corps poreux, électroniquement conducteur et électrochimiquement actif, définissant des surfaces (15, 17) en contact respectivemement avec le gaz et l'électrolyte, une membrane conductrice, ioniquement ionomère, étant disposée sur la surface en contact avec l'électrolyte (17). La membrane se compose d'une résine d'échange d'anions hydrophiles qui est sensiblement imperméable au flux du gaz.
PCT/US1988/000622 1987-03-02 1988-03-02 Membranes ionomeres pour electrodes a diffusion gazeuse supportant la pression Ceased WO1988006643A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2077787A 1987-03-02 1987-03-02
US020,777 1987-03-02

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WO1988006643A1 true WO1988006643A1 (fr) 1988-09-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2835656A1 (fr) * 2002-05-13 2003-08-08 Commissariat Energie Atomique Pile du type metal-oxygene comprenant un electrolyte apte a limiter, du cote cathodique, le passage de cations

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4090931A (en) * 1975-07-07 1978-05-23 Tokuyama Soda Kabushiki Kaisha Anode-structure for electrolysis
US4615954A (en) * 1984-09-27 1986-10-07 Eltech Systems Corporation Fast response, high rate, gas diffusion electrode and method of making same
US4732660A (en) * 1985-09-09 1988-03-22 The Dow Chemical Company Membrane electrolyzer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL291215A (fr) * 1961-04-06
SE7409783L (fr) * 1973-07-31 1975-02-03 Devices Ltd
JPS52122277A (en) * 1975-12-10 1977-10-14 Oval Eng Co Ltd Electrode
NL7607470A (en) * 1976-07-07 1978-01-10 Electrochem Energieconversie Electrodes for gaseous fuel cells - with porous electrically conducting layer and ion exchange layer, can be run on air contg. carbon di:oxide
NL7607471A (nl) * 1976-07-07 1978-01-10 Electrochem Energieconversie Elektrochemische zink-zuurstof-cel.
US4534845A (en) * 1982-08-03 1985-08-13 The Dow Chemical Company Separator-gas electrode combination

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4090931A (en) * 1975-07-07 1978-05-23 Tokuyama Soda Kabushiki Kaisha Anode-structure for electrolysis
US4615954A (en) * 1984-09-27 1986-10-07 Eltech Systems Corporation Fast response, high rate, gas diffusion electrode and method of making same
US4732660A (en) * 1985-09-09 1988-03-22 The Dow Chemical Company Membrane electrolyzer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0371965A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2835656A1 (fr) * 2002-05-13 2003-08-08 Commissariat Energie Atomique Pile du type metal-oxygene comprenant un electrolyte apte a limiter, du cote cathodique, le passage de cations

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Publication number Publication date
EP0371965A4 (fr) 1990-05-14
EP0371965A1 (fr) 1990-06-13

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