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
  • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for

Definitions

• chlor-alkali cell Within the field of electrochemistry, there is a well-known type of electrolytic cell known as a chlor-alkali cell. Basically this is a cell wherein chlorine gas and caustic soda, viz., sodium hydroxide, are produced by passing an electric current through a concentrated salt (brine) solution containing sodium chloride and water. A large portion of the chlorine and caustic soda for the chemical and plastic industries is produced in chlor-alkali cells.
• the separator characteristically can be a substantially hydraulically impermeable membrane, e.g., a hydraulically impermeable cation exchange membrane such as the commercially available NAFION O manufactured by E.I. duPont de Nemours and Co.
• the separator can be a porous diaphragm, e.g., asbestos, which can be in the form of vacuum deposited fibers or asbestos paper sheet as are well known in the art.
• the anode can be a valve metal, e.g., titanium, provided with a precious metal coating to yield what is known in the art as a dimensionally stable anode.
• the cathodes employed in such chlor-alkali cells are subjected to the corrosive environment of the caustic soda and so special precautionary measures and techniques have been employed in an attempt to reduce damage and deactivation of the active layer particles contained in the cathodes used in chlor-alkali cells.
• One known form of oxygen (air) cathode involves use of an active cathode layer containing porous active carbon particles whose activity in promoting the formation of hydroxide may or may not be catalyzed (enhanced) using precious metal catalyst materials, such as silver, platinum, etc.
• the active carbon particles become wetted (flooded) by the caustic soda thereby significantly reducing their ability to eliminate the formation of hydrogen at the cathode and resulting in a loss of activity of the air cathode.
• hydrophobic materials e.g., polytetrafluoroethylene (PTFE)
• PTFE polytetrafluoroethylene
• the cathode active layer in as much as PTFE, per se, is nonconductive when compared with the porous active carbon particles.
• Such active carbon/PTFE-containing electrode active layers are subject to loss of strength resulting in failure combined with blistering thereof when the chlor-alkali cell is operated at high current densities, viz., current densities ranging from about 250 milliamperes/cm 2 and higher for prolonged time periods.
• Some oxygen (air) cathodes contain PTFE in both the active layer and in a backing sheet laminated thereto.
• the PTFE has been employed in particulate or fibrillated (greatly attenuated and elongated) form to impart hydrophobicity to the desired layer.
• the present invention is particularly directed to an improved fibrillated matrix electrode active layer, the gas, e.g., oxygen (air) electrode containing it and a process for forming the active layer and electrode such that the resulting coherent, self-sustaining active layer sheet can be employed as the active layer when laminated to a backing (wetproofing) sheet and current collector to form an oxygen (air) cathode having high durability and resistance to degradation due to the corrosive environment present in a chlor-alkali cell, fuel cell, etc.
• the fibrillated, matrix active layer produced in accordance with this invention is capable of long life with a lower rate of decline in operating voltage.
• matrix is employed herein in as much as it is believed that in an electrode of this type, the catalyzed active carbon is thoroughly involved with assisting the reduction of oxygen within the cathode active layer while the carobn black and the PTFE act in one or more ways; (a) as a hydrophobic gas path, (b) as a conductive agent, which lowers the electrical resistance of the mixture from about 2 to 3 times, resulting in a better current distribution to the current collector, and (c) as a hydrophobic binder, incorporating the wet active carbon in a matrix of Teflon/carbon black.
• the present invention is not dependent upon this or any theory for the operation thereof.
• U.S. Patent 4,058,482 discloses a sheet material principally comprised of a polymer such as PTFE and a pore-forming material wherein the sheet is formed of co-agglomerates of the polymer and the pore former.
• This patent teaches mixing polymer particles with positively charged particles of a pore former, e.g., zinc oxide, to form co-agglomerates thereof followed by mixing same with a catalyst suspension so as to form co-agglomerates of catalyst and polymer-pore-former agglomerates followed by pressing, drying, and sintering these co-agglomerates. Subsequent to this sintering, the pore former can be leached out of the electrodes.
• a pore former e.g., zinc oxide
• U.S. Patent 4,150,076 (a division of U.S. Patent 4,058,482) is directed to the process for forming the sheet of U.S. Patent 4,058,482, said process involving formation of polymer-pore-former co-agglomerates, distributing same as a layer on a suitable electrode support plate, for example, a carbon paper, to form a fuel cell electrode by a process which includes pressing, drying, sintering, and leaching.
• U.S. Patent 4,170,540 to Lazarz et al discloses microporous membrane material suitable for electrolytic cell utilization and formed by blending particulate polytetrafluoroethylene, a dry pore-forming particulate material, and an organic lubricant. These three materials are milled and formed into a sheet which is rolled to the desired thickness, sintered, and subjected to leaching of the pore-forming material.
• the present invention avoids the use of lubricants and similarly avoids the necessity of removing same.
• special care is taken to avoid conditions which would cause the PTFE to sinter.
• the present invention is clearly distinguishable from U.S. Patent 4,170,540 in respect of preparation of the backing sheet.
• British Patent 1,284,054 to Boden et al is directed to forming an air-breathing electrode containing an electrolyte within an air-depolarized cell.
• This air-breathing electrode is made by hot pressing a fluoropolymer sheet containing a pore-forming agent onto a catalyst composition (containing silver) and a metallic grid member.
• the PTFE-pore-forming agent-paraffin wax containing sheet is subjected to a solvent wash to remove the paraffin wax and then sintered in a sintering furnace at the appropriate temperatures for sintering the fluorocarbon polymer.
• Hot pressing involves the use of pressures ranging from about 5,000 to about 30,000 psi in conjunction with temperatures ranging from about 200° to 400°F.
• the process of the present invention is readily distinguishable from British Patent 1,284,054 in that the present invention avoids the use of wax, avoids the trouble and expense of removing the wax with a solvent wash and does not use sintering thereby imparting greater porosity to the PTFE in fibrillated form in the finished electrode. Additionally the present invention avoids the repeated stripping- folding over-rolling again procedures required in all the examples of British Patent 1,284,054. It will be observed that one of the backing layers which can be laminated according to the present invention surprisingly allows the formation of a porous, self-sustaining, coherent backing sheet or layer of PTFE using only a single pass through rollers.
• U.S. Patent 3,385,780 to I-Ming Feng discloses a thin, porous electrode consisting of a thin layer of a polytetrafluoroethylene pressed against a thin layer of polytetrafluoroethylene containing finely divided platinized carbon, the platinum being present in amounts of 1.2 to 0.1 mg/cm "
• the electrically conductive face of the thin electrode viz., the side containing the platinized carbon, viz., the active layer.
• a thermally decomposable filler material can be used, or the filler can be a material capable of being leached-out by either a strong base or an acid.
• U.S. Patent 3,385,780 also mentions a single unit electrode involving finely divided carbon in mixture with PTFE.
• partially fluorinated acetylene black carbon particles are incorporated with the PTFE in the backing layer thereby resulting in improved electrical conductivity in the backing layer combined with balanced hydrophobicity.
• U.S. Patent 4,135,995 to Cletus N. Welch is directed to a cathode having a hydrophilic portion formed of a solid intercalation compound of fluorine and carbon of the emperical formula CF x where x ranges from about 0.25 to 1 and preferably ranges from about 0.25 to 0.7.
• the intercalation compounds of carbon and fluorine are referred to as hydrophilic, fluorinated graphites and graphite fluorides characterized by an infrared spectrum showing an absorption band at 1220 cm- 1.
• a layer of hydrophobic material such as polyperfluoro- ethylene (polytetrafluoroethylene) can be utilized in a hydrophobic portion of the same layer or it can be utilized in the form of a different layer which can be associated with a current carrier layer.
• the Welch cathode may be utilized as an oxygen (air) cathode.
• the present invention in respect of the backing layer is readily distinguishable from that of the Welch patents (when incorporating partially fluorinated acetylene carbon black particles) in several respects.
• the partially fluorinated compounds utilized in accordance with this invention have a hydrophobicity greater than that of the acetylene carbon black prior to partial fluorination.
• the partially fluorinated compounds which can be utilized in accordance with one embodiment of this invention are acetylene carbon blacks of the formula CF , wherein x ranges from about 0.1 to 0.18. Hence, the extent of fluorination is markedly less in these partially fluorinated compounds as compared with those disclosed by said Welch patent.
• the Welch intercalation compounds are fluorinated graphites or graphite fluorides.
• the partially fluorinated acetylene carbon balck compounds which can be used in the laminates of this invention are partially fluorinated carbon black, e.g., acetylene black, which acetylene blacks are produced by the explosive or thermal cracking of acetylene or by corresponding electrical procedures.
• acetylene carbon blacks show significant differences when compared with graphitic blacks and active carbons due to their structure and history of production.
• U.S. Patent 3,838,064 to John W. Vogt et al is directed to a process for dust control involving mixing a finely divided fibrillatable polytetrafluoroethylene with a material which characteristically forms a dust to form a dry mixture followed by sufficient working to essentially avoid dusting. Very small concentrations of PTFE, e.g., from about 0.02 to about 3% by weight, are employed to achieve the dust control.
• Corresponding U.S. Patent 3,838,092 also to Vogt et al is directed to dustless compositions containing fibrous polytetrafluoroethylene in concentrations of about 0.02% to less than 1%, e.g., about 0.75% by weight, of PTFE based on total solids.
• the active layers and laminates of this invention are also readiy distinguishable from the oxygen (air) cathodes described in Iliev et al.
• the active layer is a "matrix" layer prepared substantially by shear blending (fibrillating) a combined mixture of two separately formed mixes which are in turn mixed, chopped and then fibrillated to result in a coherent, self-sustaining sheet having a tensile strength characteristically exceeding 100 psi.
• Such active layers when laminated, yield a matrix electrode having an unusual combination of high tensile strength with resistance to blistering under high current densities in use. It will be observed that the conditions employed in formation of the two separately formed mixtures and fibrillation thereof are insufficient to affect sintering of the PTFE contained in said matrix electrode.
• the electrode described contains 2 to 8% PTFE, is produced without sintering and is composed of graphitic carbon (ACCO Graphite) or metallized graphitic carbon particles blended with a PTFE latex and a thermoplastic molding compound to form an interconnected network which enmeshes the filter particles. This blend is molded into a flat sheet and the thermoplastic is then extracted.
• the present process employs nongraphitic active carbons, significantly higher concentrations of PTFE in the active layer while avoiding the use of thermoplastic molding compound and avoiding the necessity to remove same.
• the active layer used according to this invention is formed by rolling a prefibrillated granular mix and no molding step is necessary. No indication is given by Landi et al as to the stability and/or durability of their air electrode, and no life testing or data is included in said article.
• U.S. Patent 3,368,950 discloses producing fuel cell electrodes by electrochemically depositing a uniform noble metal coating on a thin less noble metal body, for example, platinum on gold; platinum on silver; palladium on silver; gold on silver; rhodium on silver; gold on copper; silver on copper; nickel on iron or platinum on iron.
• U.S. Patent 3,352,719 is directed to a method making silver-catalyzed fuel cell electrodes by plating a silver catalyst on a carbon or nickel substrate.
• British Patent 1,222,172 discloses use of an embedded conductive metal mesh or screen 35 withn a formed electrode 30 containing a particulate matrix 34 of polytetrafluoroethylene polymer particles 21 in which there are located dispersed electrically conductive catalyst particles 24 which can be silver-coated nickel and silver-coated carbon particles, viz., two diferent types of silver-coated particles in the PTFE particulate matrix in an attempt to overcome an increase in resistance as silver is consumed in the gas diffusion fuel cells to which said British patent is directed.
• U.S. Patent 3,539,469 is directed to the use of silver-coated nickel particles (powder) in a fuel cell catalyst to economize on the use of silver.
• This patent states that silver, as an oxygen activation catalyst, has been known and heretofor used.
• the active layer of this invention is comprised of active carbon particles present within an unsintered network (matrix) bf fibrillated carbon black/PTFE.
• the laminated gas electrodes of this invention are comprised of said active layer laminated on the electrode working surface to a current distributor and on its opposite surface to a porous coherent, hydrophobic, polytetrafluoroethylene-containing wetproofing layer.
• the active carbon particles of the active layer preferably are catalyzed to contain silver or platinum and range in size from about 1 to 30 microns.
• the unsintered network (matrix) contains from about 25 to 35 weight parts of polytetrafluoroethylene and about 75 to 65 weight parts of carbon black having a surface area ranging from about 25 to 300 m 2 per gram and particle sizes ranging from about 50 to 3000 angstroms.
• the active layer contains a pore-forming agent and the concentration of active carbon therein ranges from about 40 to 80 weight %.
• the three-layer laminated electrodes produced in accordance with this invention contain an outer wetproofing or backing layer the purpose of which is to prevent electrolyte from coming through the active layer and wetting the gas side of the active layer and thereby impeding access of the oxygen (air) gas to the actie layer.
• the backing layer is a porous one containing one-pass process, viz., wherein., it is formed as acoherent, self-sustaining backing layer sheet by a single pass through heated rollers.
• the porous backing layer contains not only a pore former and polytetrafluoroethylene particles, but also contains either electroconductive carbon black particles, per se, or carbon black particles which have been partially fluorinated to certain extents of fluorination, as will be pointed out in more detail hereinafter.
• the backing layer can be prepared in accordance with the process described and claimed in copending U.S. Patent Application Serial No. 202,583 (Docket 3197) entitled "One Pass Process for Forming Electrode Backing Sheet” filed in the names of Frank Solomon and Charles Grun on October 31, 1980.
• the Teflon particles are usually employed in the form of a nonaqueous dispersion, e.g., the duPont Teflon 6A series.
• Teflon 6A for example, consists of coagulates or agglomerates having a particle size of about 500 to 550 microns which were made by coagulating (agglomerating) PTFE dispersed particles of about 0.05 to 0.5 micron and having an average particle size of about 0.2 micron.
• agglomerates are dispersed in an organic liquid medium, usually a lower alkyl alcohol, such as isopropanol, and broken down by beating, e.g., in a high speed Waring blender for about 3 minutes to redisperse same and break up the larger particles into smaller Teflon particles in isopropanol.
• pulverized sodium carbonate particles having particle sizes ranging from about 1 to about 40 microns, and more usually from about 5 to 20 microns, and preferably having an average (Fisher Sub-Sieve Sizer) particle size of 3 to 4 microns, are added to the alcohol dispersion of the blended PTFE particles in a weight ratio ranging from about 30 to 40 weight parts of PTFE to about 60 to about 70 weight parts of sodium carbonate to result in an intimate dispersion of PTFE with pore former. Then the alcohol is removed and the PTFE-Na 2 C0 3 mix particles are dried.
• the particulate PTFE-sodium carbonate mixture is subjected to sigma mixing under conditions which mildly "fiberize" (fibrillate) the PTFE.
• the sigma mixing is conducted in a Brabender Prep Center Model D101 with attached Sigma Mixer with a charge of approximately 140 grams of mix. This fibrillation is performed for approximately 10 to 20, e.g., 15, minutes at 100 rpm and 15 0 to 25°C, e.g., 20°C.
• the fibrillated PTFE-pore former mix is chopped for 1 to 20 seconds, e.g., 5 to 10 seconds.
• the mildly "fiberized” chopped mixture of PTFE--sodium carbonate is then dry rolled into sheet form using a single pass. through one or more sets of metal, e.g., chrome plated steel rolls. Temperatures of about 70° to about 90°C and roll gaps ranging from about 5 to about 15 mils are customarily employed. The conditions employed in the dry rolling are such as to avoid sintering of the PTFE particles.
• This material was then fibrillated mildly in a Brabender Prep Center D101 for 15 minutes at 100 rpm and 20°C using the Sigma Mixer Blade Model 02-09-000 as described above.
• the thus fibrillated mixture was then chopped for 5 to 10 seconds in a coffee blender (i.e., Type Varco, Inc. Model 228.1.00 made in France) to produce a fine powder.
• the chopped, fibrillated mixture was then passed through 6-inch diameter rolls, heated to about 800C and using a roll gap typically 0.008 inch (8 mils).
• the sheets are formed directly in one pass and are ready for use as backing layers in forming electrodes, e.g., oxygen cathodes, with no further processing beyond cutting, trimming to size and the like.
• the thus formed layers are characterized as porous, self-sustaining, coherent, unsintered uniaxially oriented backing (wetproofing) layers of fibrillated polytetrafluoroethylene having pore openings of about 0.1 to 40 microns (depending on the size of the pore-former used) and exhibit air permeability particularly well suited for oxygen (air) cathodes.
• Example 1 The procedure of Example 1 was repeated with the exception that after the PTFE/Na 2 C0 3 sheet was passed through the rollers once it was folded in half and re-rolled in the same direction as the original sheet. A disc of this material was pressed at 8.5 tons per square inch and 115°C and then washed with water to remove the soluble pore former. Permeability tests conducted on this sample resulted in a permeability of 0.15 ml of air/minute/cm 2 at a pressure of one cm of water as compared to a test sample prepared according to Example 1 and pressed and washed as above which gave a permeability of 0.21 ml of air/minute/cm-/cm of water.
• the permeability test was done according to the method of A.S.T.M. designation E 128-61 (Maximum Pore Diameter and Permeability of Rigid Porous Filters for Laboratory Use) in which the test equipment is revised to accept discs for test rather than the rigid filters for which the test was originally designed.
• the revision is a plastic fixture for holding the test disc in place of the rubber stopper shown in Figs. 1 and 2 of said A.S.T.M. standard.
• folding and re-rolling are counter productive to air permeability, an important and desired property in a backing layer for an oxygen cathode.
• folding and re-rolling may form laminae which give rise to delamination of the backing layer in use, e.g., in a chlor-alkali cell.
• a porous Teflon sheet was fabricated using a mixture of 40 weight % ammonium benzoate (a volatile pore former) and 60 weight % PTFE prepared as in Example 1.
• the sheets were fabricated by passing the above mix (fibrillated and chopped) through the 2 roll mill once. The rolled sheet was then pressed at 8.5 tons per square inch and 65°C. The volatile pore former was then removed by heating the sheet in an oven at 150° C . Substantially, all of the volatile pore former was thus sublimed leaving a pure and porous PTFE sheet. Permeability of these sheets average 0.2.
• the laminate has a backing layer containing carbon particles to enhance the conductivity thereof
• carbon blacks unmodified carbon blacks or partially fluorinated carbon blacks, e.g., partially fluorinated acetylene black particles, can be utilized to impart conductivity to the backing layer.
• carbon blacks When utilizing unfluorinated carbon black particles to impart the conductivity to the PTFE-containing porous backing layer, carbon blacks can be employed which are electrically conductive.
• the term carbon black is used generically as defined in an article entitled “Fundamentals of Carbon Black Technology” by Frank Spinelli appearing in the August 1970 edition of American Print Maker to include carbon blacks of a particulate nature within the size range of 5 to 300 millimicrons which includes a family of industrial carbons such as lampblacks, channel blacks, furnace blacks, thermal blacks, etc.
• a preferable form of unmodified (unfluorinated) carbon black is acetylene carbon black, e.g., made from acetylene by continuous thermal decomposition, explosion, by combustion in an oxygen-deficient atmosphere, or by various electrical processes.
• acetylene black contains 99.5+ weight percent carbon and has a particle size ranging from about 50 to about 2000 angstrom units.
• the true density of the acetylene black material is approximately 1.95 grams per cubic centimeter.
• the acetylene black is a commercially available acetylene black known by the designation "Shawinigan Black" and has a mean particle size of 425 angstroms with a standard deviation of about 250 angstroms.
• Such acetylene blacks are somewhat hydrophobic, e.g., as demonstrated by the fact that the particles thereof float on cold water but quickly sink in hot water.
• the hydrophobic electroconductive electrode backing layers were prepared in accordance with this invention by combining the PTFE in particulte form as a dispersion with the carbon black particles as described above.
• the acetylene carbon black employed is that having an average particle size of approximately 435 angstrom units with the remainder having a standard deviation of 250 angstrom units.
• the range of particle size is from about 50 to about 2000 angstroms.
• acetylene black particles are mixed with PTFE particles by adding a commercially available aqueous dispersion, e.g., duPont "Teflon 30" to the carbon black, also dispersed in water to form an intimate mixture thereof.
• the "Teflonated” mix can contain from about 50 to about 80 weight % carbon black and from about 20 to about 50 weight % PTFE. Water is removed and the mix is dried. The dried Teflonated mix can then be heated at 275° to 300°C for 10 to 80 minutes to remove a substantial portion of the wetting agent used to disperse the PTFE in water.
• Such conductive PTFE/carbon black-containing backing layers characteristically have thicknesses of 5 to 15 mils and may be produced by filtration or by passing the aforementioned acetylene black-PTFE mixes through heated rollers at temperatures of 65 0 to 90 0 C or by any other suitable technique.
• these backing layers are laminated with a current distributor and the active layer as disclosed herein.
• SB Shawihigan Black
• a PTFE/SB conductive, hydrophobic wetpoofing layer or sheet was prepared by the filtration method as follows: 225 milligrams of the PTFE discontinuously coated SB, prepared in accordance with Example 1, were chopped in a small high speed coffee grinder (Varco Model 228-1, made in France) for about 30 to 60 seconds and then dispersed in 250 mls of isopropyl alcohol in a Waring blender. This dispersion was then filtered onto a "salt paper," viz., NaCl on filter paper, of 17 cm 2 area to form a cohesive, self-sustaining wetproofing layer having 10.6 mg/cm2 by weight (20 mg total).
• Resistivity of this wetproofing layer was measured and found to be 0.53 ohm-centimeters.
• the resistivity of pure PTFE (from “Teflon 30") is greater than 10 ohm-cm by way of comparison.
• the resistivity of the PTFE/SB carbon black wetproofing layer illustrates that it is still low enough to be useful in forming electrodes when in intimate contact with a current distributor.
• Permeability is an important factor in high current density operation of a gas electrode having hydrophobic (conductive or nonconductive) backing, viz., a wetproofing or liquid barrier layer.
• the wetproofing layers employed in forming laminates according to this invention have adequate permeability to be comparable to that of pure PTFE backings (even when pressed at up to 5 tons/in 2 ) yet have far superior electroconductivity.
• the active carbon can be conditioned and used with or without a precious metal catalyst, e.g., platinum, silver, etc., on and/or within the pores thereof by the procedures described and claimed in accordance with U.S. Patent Applications Serial Nos. 202,579 and 202,580 (Dockets 3193 and 3994) filed in the name of Frank Solomon on October 31, 1980, and having the titles "Process for Catalyst Preparation" and "Active Carbon Conditioning Process," U.S. Patent Application Serial No. 202,572 (Docket 3201) filed on October 31, 1980, in the name of Lawrence J. Gestaut and entitled "Post Platinizing High Surface Carbon Black.”
• partially fluorinated carbon black e.g., the partially fluorinated carbon black backing layers as disclosed and claimed in U.S. Patent Application Serial No. 202,582 (Docket 3196) filed in the names of Frank Solomon and Lawrence J. Gestaut and entitled “Electrode Backing Layer and Method of Preparing” and filed on October 31, 1980.
• Such partially fluorinated carbon blacks are preferably acetylene blacks which are subjected to partial fluorination to arrive at compounds having the formula CF , wherein x ranges from about 0.1 to about 0.18.
• hydrophobicity of the already hydrophobic acetylene black particles is enhanced by such partial fluorination as was observed from comparative experiments wherein the unfluorinated acetylene black particles floated on cold water but quickly sank in hot water versus the partially fluorinated acetylene blacks, fluorinated to the extent of x being about 0.1 to about 0.18, which floated on hot water virtually indefinitely and could not be made to pierce the meniscus of the water.
• the acetylene black employed is that having an average particle size of approximately 425 angstrom units with a standard deviation of 250 angstrom units. The range of particle size is from about 50 to about 2000 angstroms.
• the partially fluorinated carbon black particles are suspended in isopropyl alcohol and a dilute aqueous dispersion of PTFE (2 weight % PTFE) is added gradually thereto.
• the PTFE/CF 0.1 to 0 are examples of PTFE (2 weight % PTFE)
• the "Teflonated" mix can contain from about 50 to 80 weight % CF 0 . 1 to 0 . 18 and about 20 to 50 weight % PTFE.
• a pore former can be incorporated into the CF 0.1 to 0.18 /PTFE mix prior to forming the wetproofing layer or sheet.
• the pore former can be of the soluble type, e.g., sodium carbonate or the like, or the volatile type, e.g., ammonium benzoate or the like.
• the pore former can be removed by washing (if a soluble one) or heating (if a volatile one) either prior to laminating the wetproofing layer to the current distributor (with the distributor on the gas side) and active layer, or after lamination thereof.
• the laminate is preferably given a hot (50° to about 100°C) soak in an alkylene polyol, e.g., ethylene glycol or the like, prior to water washing for 10 to 60 minutes.
• the ethylene glycol hot soak combined with water washing imparts enhanced resistance of such laminated electrodes to blistering during water washing and is the subject matter described and claimed in U.S. Patent Application Serial No. 202,573 (Docket 3200) entitled "Electrode Layer Treating Process" and filed on October 31, 1980, in the name of Frank Solomon.
• the wetproofing layer When the wetproofing layer is formed by filtration, it can be released from the filter media by washing with water to dissolve the salt bed, drying and pressing lightly to consolidate same, followed by laminating to the current distributor and active layer.
• the filter paper/salt/wetproofing layer can be laminated to the current distributor and active layer (with the filter paper side away from the current distributor and the wetproofing layer side in contact with the current distributor) followed by dissolving the salt away.
• SBF partially fluorinated carbon-containing backing layers
• a layer was made by a filtration method. Of the above material, 225 mg was chopped in a small high speed coffee grinder, then dispersed in 250 ml isopropyl alcohol in a Waring blender and filtered onto a sodium chloride (salt) layer deposited on a filter paper of 19 cm 2 area to form a layer having an area density of 10.6 mg/cm 2. Resistivity was measured and found to be 8.8 ohm-cm.
• the SB control strip was prepared in accordance with Examples 4 and 5 above. Resistivity of this SB control strip was found to be 0.53 ohm-cm. Although the resistivity of the SBF strip is 16.6 times as great as that of said control strips, it is still low enough to be useful when a mesh conductor is embedded in the hydrophobic backing. Pure PTFE has a resistivity of greater than 10 15 ohm-cm by way of comparison.
• Gas permeability is an important property for high current density operation of a gas electrode having a hydrophobic conductive or nonconductive backing layer.
• the SBF-PTFE backing layer prepared as above had adequate air permeability comparable to the "one pass" PTFE backings of Examples -1 and 3 above even when pressed to 5 tons per square inch.
• matrix active layer comprises active carbon particles present within an unsintered network (matrix) of fibrillated carbon black/polytetrafluoroethylene.
• One stream (mixture), the matrixing mix component, is obtained by adding a dilute dispersion containing polytetrafluoroethylene (PTFE), e.g., duPont "Teflon 30" having a particle size of about from 0.05 to 0.5 micron in water to mix of a carbon black, e.g., an acetylene black, and water in a weight ratio of from about 25 to 35 weight parts of PTFE to from about 65 to 75 weight parts of carbon black to "Teflonate" the carbon black, viz., form an intimate mix of PTFE/carbon black particles, drying the aforementioned mixture and heat treating it to remove the PTFE wetting agent thereby resulting in a first component mix.
• PTFE polytetrafluoroethylene
• the second component, the active carbon-containing catalyst component is comprised of an optionally catalyzed, preferably previously deashed and optionally particle size classified active carbon, having a particle size ranging from about 1 to about 30 microns and more usually from about 10 to about 20 microns.
• Deashing can be done by pretreatment with caustic and acid to remove a substantial amount of ash from the active carbon prior to catalyzing same.
• ash refers to oxides principally comprised of silica, alumina, and iron oxides.
• the deashing of active carbon constitutes the subject matter of copending U.S. Patent Application Serial No. 202,580 (Docket 3194) entitled "Active Carbon Conditioning Process,” filed on October 31, 1980, in the name of Frank Solomon as inventor.
• the thus deashed, classified, active carbon particles can then be catalyzed with a precious metal, e.g., by contacting with a silver or platinum precursor, followed by chemical reduction with or without heat to deposit silver, platinum or other respective precious metal on the active carbon.
• the catalyzed carbon can be filtered, dried at temperatures ranging from about 80° to 150°C, with or without vacuum, to produce a second (active carbon catalyst) component or mixture.
• This mixtures are then chopped together, with or without the addition of a particulate, subsequently removable (fugitive) pore-forming agent and then shear blended (fibrillated) at temperatures ranging from about 40° to about 60°C for 2 to 10 minutes, e.g., 4 to 6 minutes, in the presence of a processing aid or lubricant, e.g., a 50:50 mixture (by weight) of isopropyl alcohol and water, viz., when no pore former is used as bulking agent.
• a processing aid or lubricant e.g., a 50:50 mixture (by weight) of isopropyl alcohol and water, viz., when no pore former is used as bulking agent.
• the lubricant can be isopropyl alcohol.
• the previously chopped mixture can be fibrillated using a mixer having a Sigma or similar blade.
• the chopped mixture of the two-component mixes is subjected to shear blending forces, viz., a combination of compression and attenuation which has the effect of substantially lengthening the PTFE in the presence of the remaining components.
• shear blending forces viz., a combination of compression and attenuation which has the effect of substantially lengthening the PTFE in the presence of the remaining components.
• This fibrillation is believed to substantially increase the strength of the resulting sheets formed from the fibrillated mixed components.
• the mixture is noted to be fibrous and hence the term "fiberizing" is used herein as synonymous with fibrillating.
• the mixture is dried, chopped for from I to 10 seconds into a fine powder and formed into a sheet by rolling at 50° to 100°C or by deposition on a filter.
• a pore former if one is employed as a bulking agent; can be then removed prior to electrode fabrication.
• the matrix active layer sheet can be used (as is) as the active catalyst-containing layer of an oxygen (air) cathode, e.g., for use in a chla-alkali cell fuel cell, etc.
• the aforementioned blistering and structural strength problems encountered at high current densities in the active layers of gas electrodes can be substantially overcome by a process involving: forming two separate components, one a matrixing mix component containing carbon black with polytetrafluoroethylene particles and heat treating this PTFE-carbon black mix at given temperature conditions; separately forming an active carbon-containing catalyst component; combining these two separate components into a mix; chopping the mix and shear-blending the chopped mix (fibrillating same) in order to arrive at a readily formable matrix which can be formed, e.g., pressed between rolls, or deposited upon a filter paper as a forming medium, pressed and then used as the active layer in an oxygen (air) cathode.
• Such process results in active layers having reduced carbon corrosion, higher conductivity and air-transport combined with strength when compared with prior structures. This results in electrodes which can be used longer and are more stable in use.
• a water-soluble pore-forming agent e.g., sodium carbonate
• the pore-forming agent can be added later, when the carbon black-PTFE mix and the catalyzed active carbon particles are mixed together and chopped.
• the usual particle size of the carbon black ranges from about 50 to about 3000 angstroms and it has a surface area ranging from about 25 to about 300 m2/gram.
• the PTFE is preferably employed in aqueous dispersion form and the mixture of carbon black and polytetrafluoroethylene can contain from about 65 to about 75 weight parts of carbon black and about 35 to about 25 weight parts of PTFE.
• the carbon black and PTFE are dried and then the dried initial mix is heated in air at temperatures ranging from about 250° to 325°C, and more preferably 275° to 300°C,-for time periods. ranging from 10 minutes to 1.5 hours and more preferably from 20 minutes to 60 minutes. This heating removes the bulk of the PTFE wetting agent.
• the other component of the matrix electrode viz., the active carbon, preferably "RB" carbon manufactured by Calgon, a division of Merck, is deashed by contact with an aqueous alkali, e.g., sodium hydroxide, or equivalent alkali, and more usually aqueous sodium hydroxide having a sodium hydroxide concentration of about 28 to about 55 weight % for 0.5 to 25 hours.
• an aqueous alkali e.g., sodium hydroxide, or equivalent alkali
• an acid which can be hydrochloric acid, phosphoric acid, sulfuric acid, hydrobromic acid, etc., at ambient temperatures using aqueous acid solutions having from about 10 to about 30 weight % acid, based on total solution for comparable time periods.
• the deashed active carbon particles are preferably catalyzed.
• the deashed particles are preferably catalyzed as by contact with a precursor of a precious metal catalyst.
• a precursor of a precious metal catalyst In the event that silver is desired to be deposited within the pores of the active carbon, it is preferred to use silver nitrate as the catalyst precursor followed by removal of excess silver and chemical reduction with alkaline formaldehyde. Theis can be done as. described and claimed in U.S. Patent Application Serial No. 202,579 (Docket 3193) entitled "Process for Catalyst Preparation" filed on October 31, 1980, in the name of Frank Solomon.
• chloroplatinic acid can be used as a precursor followed by removal of excess chloroplatinic acid and chemical reduction using sodium borohydride or formaldehyde as a 'reducing agent.
• the platinum is derived from H 3 Pt(SO 3 ) 2 OH by the procedure set forth in U . S . Patent 4,044,193. The reduction can be accompanied with the use of heat or it can be done at ambient room temperatures.
• the active carbon particles are filtered and vacuum dried as the active carbon-containing catalyst component in preparation for combination with the acetylene black/PTFE matrixing component mix.
• the carbon black/PTFE matrixing component mix preferably in a weight ratio ranging from about 65 to 75 weight parts of carbon black to 25 to 35 weight parts of PTFE is mixed with the catalyzed deashed active carbon-containing component and subjected to chopping to blend the carbon black/PTFE matrixing component with the catalyst component in the manner set forth above.
• This mix is then subjected to fibrillation (shear blending or fiberizing), for example, in a mixer with appropriate blades at approximately 50°C.
• This shear blended material has a combination of good conductivity and high tensile strength with low Teflon content resulting in extraordinarily long life in use at high current densities in the corrosive alkaline environment present in a chlor-alkali cell.
• the active layers employed in this invention can contain (after removal of any pore-forming bulking agent therefrom) from about 40 to 80 weight % of active carbon, the remainder being the matrixing materials, carbon black and PTFE.
• Active carbon-containing active layer sheets produced in accordance with this invention characteristically have thicknesses of 0.010 to 0.025 inch (10 to 25 mils) with corresponding tensile strengths ranging from about 75 to 150 psi (measured after pressing in a hydraulic press at 8.5 T/in2and 112°C for 3 minutes).
• RB carbon Commercially available ball milled "RB carbon” was found to have an ash content of approximately 12% as received. This "RB carbon” was treated in 38% KOH for 16 hours at 115°C and found to contain 5.6% ash content after a subsequent furnace operation. The alkali treated “RB carbon” was then treated (immersed) for 16 hours at room temperature in 1:1 aqueous hydrochloric acid (20% concentration). The resulting ash content had been reduced to 2.8%. "RB carbon,” deashed as above, was silvered in accordance with the following procedure:
• “Shawinigan Black” a commercially available acetylene carbon black was teflonated with “Teflon 30” (duPont polytetrafluoroethylene dispersion) using an ultrasonic generator to obtain intimate mixture. 7.2 grams of the carbon black/PTFE mix was high speed chopped, spread in a dish, and then heat treated at 525°F for 20 minutes. Upon removal and cooling, it was once again high speed chopped, this time for 10 seconds. Then 18 grams of the classified silvered active carbon was added to the 7.2 grams of carbon black-Teflon mix, high speed chopped for 15 seconds, and placed into a fiberizing (fibrillating) apparatus.
• Teflon 30 duPont polytetrafluoroethylene dispersion
• the apparatus used for fiberizing consists of a Brabender Prep Center, Model D101, with an attached measuring head REO-6 on the Brabender Prep Center and medium shear blades were used.
• the mixture was added to the cavity of the mixer using 50 cc of a 30/70 (by volume) mixture of isopropyl alcohol in water as a lubricant to aid in fibrillating.
• the mixer was then run for 5 minutes at 30 rpm at 50°C, after which the material was removed as a fibrous coherent mass. This mass was then oven dried in a vacuum oven and was high speed chopped in preparation for rolling.
• the chopped particulate material was then passed through a rolling mill, a Bolling rubber mill.
• the resulting matrix active layer sheet had an area density of 22.5 milligrams per square centimeter and was ready for lamination.
• Example 7 The procedure of Example 7 was repeated except that platinum wa: deposited on the deashed active ("RB”) carbon instead of silver.
• the 10 to 2t micron classified deashed "RB” carbon had platinum applied thereto in accordance with the procedure described in U.S. Patent 4,044,193 using H 3 Pt(SO 3 ) 2 OH to deposit 1 weight part platinum per 34 weight parts of deashed active carbon.
• the area density of the active layer was determined to be 22.2 milligrams per -cm2. This matrix active layer was then ready for lamination.
• An active layer containing deashed, silvered "RB” active carbon was prepared as in Example 7 with the exception that the 70/30 (by weight) "Shawinigan Black”/"Teflon 30" matrixing material was not heat treated before fibrillating.
• This matrix active layer was heavier than those prepared according to Example 7 and 8. It had an area density of 26.6 milligrams per cm 2 and was ready for lamination.
• This matrix active layer was made according to the basic procedure of Example 7 using deashed “RB” active carbon platinized by the method of U.S. Patent 4,044,193 to a level of 19 weight parts of deashed “RB” active carbon per weight part platinum.
• Six grams of ultrasonically teflonated (70:30, "Shawinigan Black”:PTFE) carbon black were heat treated for 20 minutes at 525 0 F prior to addition thereto of 15 grams of said active carbon along with 9 grams of sodium carbonate, which had been classified to the particle size range of +5 to -10 microns.
• This material was fibrillated and rolled out as in Example 1 and extracted by water (to remove the sodium carbonate) after first hot soaking it in ethylene glycol at 75°C for 20 minutes.
• the resulting active layer sheet was a very porous and lightweight material.
• the current distributor layer which is usually positioned next to and laminated to the working surface of the active layer of the three-layer laminate, can be an asymmetric woven wire mesh wherein the material from which the wire is made is selected from the group consisting of nickel, nickel-plated copper, nickel-plated iron, silver-plated nickel, and silver-plated, nickel-plated copper and like materials.
• the material from which the wire is made is selected from the group consisting of nickel, nickel-plated copper, nickel-plated iron, silver-plated nickel, and silver-plated, nickel-plated copper and like materials.
• the current distributor or collector utilized in accordance with this invention can be a woven or nonwoven, symmetrical or asymmetric wire mesh or grid. Generally there is a preferred current carrying direction. When the current distributor is a copper wire mesh, there should be as few wired as feasible in the noncurrent carrying direction. There will be found to be ⁇ minimum required for fabrication of a stable wire cloth. A satisfactor) asymmetric wire cloth configuration may consist of, e.g., 50 wires/inch in the warp direction but only 25 wires per inch in the fill, thus enhancing the economy and utility of the wire cloth, simultaneously.
• the current distribuor can be of the plaque type, viz., ; comparatively compact yet porous layer, having porosities ranging from about 3 1 to about 80% and made of powders of Ni, Ag or the like.
• the three-layer laminates produced in accordance with this inventio usually have the active layer centrally located, viz., positioned in the middl between the backing layer on the one side and the current distributor (collector layer on the other side.
• the three layers arranged as described are laminate using heat and pressure at temperatures ranging from about 100° to about 130°( and pressures of 0.5 to 10 T/in followed by removal from the pressing device.
• the laminates are preferably then subjected to a hot soaking step in ethylen glycol or equivalent polyol to enhance removal of the pore-forming agent(s) employed to form the aforementioned backing (wetproofing) layer and any bulking and/or pore-forming agent optionally included in the active layer, upon subsequent washing(s) with water.
• the laminating pressures used will depend on whether or not electroconductive (carbon black) particles have been included in the backing layer along with the PTFE. Thus wheh using pure Teflon, viz., Teflon with pore former only, pressures of 4 to 8 T/in 2 and temperatures of 90° to 130°C are customarily employed. Upon lamination, the current collector is deeply embedded in the active layer.
• the three-layer laminates of this invention can be formed using a variety ' of the aforementioned backing layers and current distributors.
• the following examples further illustrate their preparation and actual testing in corrosive alkaline environments and at current densities such as are employed in chlor-alkali cells, fuel cells, batteries, etc.
• This mixture was mildly fibrillated in a Brabender Prep Center with attached Sigma mixer as described above.
• the fibrillated material is chopped to a fine dry powder using a coffe blender, i.e., Type Varco, Inc. Model 228.1.00 made in France.
• Chopping to the desired extent takes from about 5 to 10 seconds because the mix is friable. The extent of chopping can be varied as long as the material is finely chopped.
• the chopped PTFE-NaC0 3 mix is fed to 6-inch diameter chrome- plated steel rolls heated to about 80°C. Typically these rolls are set at a gap of 0.008 inch (8 mils) for this operation.
• the sheets are formed directly in one pass and are ready for use as backing layers in forming electrodes, e.g., oxygen cathodes, with no further processing beyond cutting, trimming to size and the like.
• the current distributor was a 0.004 to 0.005 inch diameter nickel woven wire mesh having a 0.0003 inch thick silver plating and the woven strand arrangement tabulated below.
• the distributor was positioned on one active layer side while the backing layer was placed on the other side of the active layer.
• the lamination was performed in a hydraulic press at 100° to 130°C and using pressures of 4 to 8.5 T/in 2 for several minutes. These laminates were then hot soaked in ethylene glycol at 75°C for 20 minutes.before water washing at 65°C for 18 hours and then dried.
• the laminates were then placed in respective half cells for testing against a counter electrode in 30% aqueous sodium hydroxide at temperatures oi 70° to 80°C with an air flow of 4 times the theoretical requirement for an ai cathode and at a current density of 300 milliamperes per cm 2.
• the testing results and other pertinent notations are given below.
• a laminated electrode was formed using the PTFE/sodium carbonate one pass backing layer of Example 1, the active layer of Example 7 and a prior art type porous sintered nickel plaque current distributor (Dual Porosity Lot No. 502-62-46).
• the matrix active layer was positioned on the coarse side of said plaque and the PTFE/sodium carbonate backing layer was placed on top of the other surface of the active layer.
• This sandwich was pressed at 8.5 T/in 2 and 115 0 C for 3 minutes after which it was hot soaked in ethylene glycol at 75°C for 20 minutes followed by water washing at 65 0 C for 18 hours.
• This air electride was operated at 4 times theoretical air and 250 milliamperes/cm in 30% NaOH at 70°C and operated satisfactorily for 17 days before failure.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Inert Electrodes (AREA)
• Electrodes For Compound Or Non-Metal Manufacture (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (2)

Family

ID=26897821

Family Applications (1)

Country Status (4)

Cited By (3)

Citations (3)

Family Cites Families (6)

• 1981
  • 1981-10-13 CA CA000387770A patent/CA1214753A/fr not_active Expired
  • 1981-10-28 DE DE8181305089T patent/DE3175831D1/de not_active Expired
  • 1981-10-28 EP EP81305089A patent/EP0051435B1/fr not_active Expired
• 1988
  • 1988-10-31 JP JP63275977A patent/JPH01152290A/ja active Pending

Patent Citations (3)

Also Published As

Similar Documents

Legal Events