CA1147291A - Ion exchange membrane type electrolytic cell - Google Patents
Ion exchange membrane type electrolytic cellInfo
- Publication number
- CA1147291A CA1147291A CA000359278A CA359278A CA1147291A CA 1147291 A CA1147291 A CA 1147291A CA 000359278 A CA000359278 A CA 000359278A CA 359278 A CA359278 A CA 359278A CA 1147291 A CA1147291 A CA 1147291A
- Authority
- CA
- Canada
- Prior art keywords
- exchange membrane
- electrolytic cell
- cation exchange
- cell according
- electrode layer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE:
An electrolytic cell has a gas-liquid permeable porous electrode layer on a cation exchange membrane. The electrode layer is formed by printing a paste comprising an electrode powder on the surface of said cation exchange membrane by a screen print-ing process and bonding it.
An electrolytic cell has a gas-liquid permeable porous electrode layer on a cation exchange membrane. The electrode layer is formed by printing a paste comprising an electrode powder on the surface of said cation exchange membrane by a screen print-ing process and bonding it.
Description
7~29~L
The present invention re]ates to an electrolytic cell having a cation exchange mernbrane. More particularly, the present invention relates to an electrolytic cell which is formed by bonding a porous, gas-liquid permeable, electrode layer to a cation exchange membrane and is suitable for the electrolysis of an aqueous solution of an alkali metal chloride.
As a process for producing an alkali metal hydroxide by electrolysis of an aqueous solution of an alkali metal chloride, the diaphragm method has been mainly employed instead of the mercury method to reduce pol]ution. It has been proposed to use an ion exchange membrane in place of asbestos as the diaphragm to produce the alkali metal hydroxide by electrolyzing an aqueous solution of an alkali rnetal chloride so as to obtain an alkali metal hydroxide having high purity and high concen-tration. It is also desirable to save energy and for this minimization of cell voltage is desirable.
It has been proposed to attain electrolysis by a so-called solid polymer electrolyte type electrolysis of an alkali metal chloride wherein a cation exchange membrane made of a fluorinated polymer is bonded with gas-liquid permeable catalytic anode on one surface and a gas-liquid permeable catalytic cathode on the other surface of the membrane (British Patent
The present invention re]ates to an electrolytic cell having a cation exchange mernbrane. More particularly, the present invention relates to an electrolytic cell which is formed by bonding a porous, gas-liquid permeable, electrode layer to a cation exchange membrane and is suitable for the electrolysis of an aqueous solution of an alkali metal chloride.
As a process for producing an alkali metal hydroxide by electrolysis of an aqueous solution of an alkali metal chloride, the diaphragm method has been mainly employed instead of the mercury method to reduce pol]ution. It has been proposed to use an ion exchange membrane in place of asbestos as the diaphragm to produce the alkali metal hydroxide by electrolyzing an aqueous solution of an alkali rnetal chloride so as to obtain an alkali metal hydroxide having high purity and high concen-tration. It is also desirable to save energy and for this minimization of cell voltage is desirable.
It has been proposed to attain electrolysis by a so-called solid polymer electrolyte type electrolysis of an alkali metal chloride wherein a cation exchange membrane made of a fluorinated polymer is bonded with gas-liquid permeable catalytic anode on one surface and a gas-liquid permeable catalytic cathode on the other surface of the membrane (British Patent
2,009,795). This method is very advantageous for electrolysis at a lower cell voltage because the electric resistance caused by the electrolyte and the electric resistance caused by bubbles of hydrogen gas and chlorine gas generated in the electrolysis, which have been considered to be difficult to reduce the electrolysis, can be substantially decreased. The contact of the gas-liquid permeable porous electrode with the cation exchange membrane is an important factor for the efficiency of the electrolytic cell in such solid polymer electrolyte type cation exchange membrane electrolytic cell. When -the thickness of the 7~9~
electrode is non-uniform or a contact between the electrode with the cation exchange membrane is not satisfactory, a part of the electrode is easily peeled off whereby a cell voltage increases or the gas and the solution remain in the interfaces to cause the increase of the cell vo]tage. The desired advantages of the electrolytic cell are decreased or lost.
-2a-The present invention provides a cation exchange membrane type electrolytic cell having excellent character-istics which is formed by bonding electrodes having a uniforrr thickness to a cation exchange membrane without any gap by a novel means for bonding the gas-liquid permeable porous electrode to the cation exchange memhrane, In accordance wi th the present invention a cation exchange membrane type electrolytic cell i s provided which is formed by bonding each gas-liquid permeable porous electrode to a cation exchange membrane by a screen printing process using a paste comprising an electrode powder.
' .
In the screen printing process for bonding the electrode layer to the cation exchange membrane, a paste comprising an ele-trode powder is used.
`r~ The electrodes can be formed by any material for the anode and the cathode, The anode is preferably formed by one or more platinum group metal such as platinum, ruthenium, rhodium, and iridium and electroconductive oxides thereof, and electroconductive reduced oxides thereof. The cathode is preferably formed by one or more of iron, nickel, stainless steel, a thermally decomposed product of a fatty acid nickel salt, Raney nickel, stabilized Raney nickel, carbonyl nickel and carbon powder supporting a platinum group metal.
~7;291 ,:
The electrode powder is incorporated in the paste in the form of a powder having a particle diameter of 0. 01 to 300~ especially 0,1 to 100/~. A hydrophobic polymer is preferably incorporated in the paste. The hydrophobic polymer is used as a binder for the electrode and the cation exchange rnembrane, Suitable hydrophobic .' polymers include fluorocarbon polyrners ~such as polytetrafluoro-ethylene and polyhexylfluoroethylene. The hydrophobic polymer having a particle diameter of 0 1 to 500fc/especially 0. 1 to 100~ is preferably incorporated so as to be thoroughly dispersed in the paste. In order to improve the dispersibility, it is preferable to incorporate a long chain hydrocarbon type surfactant or a fluorinated hydrocarbon type surfactant at a desired ratio The contents of the electrode powder and the hydrophobic polymer in the paste depend upon the characteristics of the ele-ctrode. The former is preferably in a range of 20 to 95 wt. %/
especially 40 to 90 wt. %. The latter is preferably in a range of 0. 1 to 80 wt, %/ especially 1 to 60 wt. % The viscosity of the paste . comprising the electrode powder is preferably controlled in the range of 1 to 105 poises/especially 10 to 104 poises before the screen printing.
The viscosity can be controlled by selecting particle sizes and contents of the electrode powder and the hydrophobic polymer and the content of water as the medium and preferably controlled in said range by incorporatin~ a viscosity regulating agent, The viscosity regulating agents may be water soluble viscous materials which are gradually soluble in water. Suitable viscosity regulating agents include cellulose type materialsj such as carboxy-methyl cellulose, methyl cellulose, hydroxyethyl cellulose, and cellulose and polyethyleneglycol polyvinyl alcohol, polyvinyl pyrro-lidone, sodium polyacrylate and polymethyl vinyl ether.
11~7~
The properties of the electrode do not deteriorate by the in-corporation of the viscosity regulating agent because of its ; water solubility. It is also possible to use any material which does not deteriorate the electrolytic characteristics by re-action or corrosion of the electrode layer in the preparation and the use of the electrode layer, such as casein and poly-acrylamide.
The paste is printed on and bonded to the surface of the cation exchange membrane by the screen printing process.
The conventional screen printing process can be employed. It is preferable to use a screen having a mesh number of 10 to 2400, especially a mesh number of 150 to 1000 and a thickness of 2 mm to 4~ , especially 300~ to 8~ hen the mesh is too large, clog-ging of the screen occurs with non-uniform printing. When the mesh is too small, excess of the paste is printed. When the thickness is too thick, non-: uniform printing is caused. When the thickness is too small, printing for a desired amount of paste is not attained. A screen mask is used for forming the electrode layer having a desired size and configuration on the - surface of the cation exchange membrane. The configuration is preferably a printed pattern eliminating the configuration of the electrode. The thickness of screen mask is preferably in the range of 1 to 500~ . The substances for the screen and the screen mask can be any materials having satisfactory strength such as stainless steel, polyethyleneterephthalate and nylon for the screen and epoxy resins for the screen mask.
A screen and the screen mask are placed on the cation exchange membrane for the printing of the electrode layer. The paste is fed on the screen and is printed under a desired pressure by squeezing whereby the electrode layer having the configuration determined by the screen mask is formed on the surface of the cation exchange membrane. The thickness of the electrode layer on the cation exchange membrane depends upon the 7~9~l thickness of the screen, the viscosity of the paste and the mesh number of the screen. It is preferable to control the thickness of the screen, the viscosity of the paste and the mesh of the screen so as to give the thickness of the electrode ranging from 0.1 to 100~, especially 1 to 50~.
; The gap between the screen and the cation exchange membrane and the material being squeezed and the pressure applied to mesh by the squeezing in the screen printing process greatly determine the physical properties, thickness and uniformity of o the electrode layer formed on the surface of the cation exchange membrane. In order to give desired printing, the gap between the screen and the cation exchange membrane is set depending upon the type and viscosity of the paste, preferably ranging from 0.5 mm to 5 cm, and the hardness of the squeeze having a sharp corner is selected according to the viscosity of the paste, -~ preferably ranging from 50 to 100 shore hardness, and the uni-form pressure of the squeeze is applied to the mesh. Thus the electrode layer having uniform thickness is formed on one or both of the surfaces of the cation exchange membrane at a high bonding strength. Thereafter it is preferable to press the electrode layer on the surface of the cation exchange membrane at 100 to 300C, and especially 110 to 250~C under a pressure of 5 to 1000 kg/cm2 and especially 20 to 500 kg/cm2 whereby a strongly bonded structure of the electrode layer and the cation exchange membrane can be obtained.
The electrode layer formed on the cation exchange membrane should be a gas permeable porous layer. The average pore diameter is preferably in the range of 0.01 to 50 ~, especially 0.1 to 30f~. The porosity is preferably in the range of 10 to 99%, especially 20 to 95%. The thickness is preferably in the range of 0.1 to 100/~-, especially 1 to 50~.
The cation exchange membrane on which the electrode 1~47~9iL
layer is formed may be made of a polymer having cation exchange groups such as carboxylic acid groups, sulfonic acid groups, - 6a -7'~1 ,, phosphoric acid groups and phenolic hydroxy groups. Suitable polymers include copolymers of a vinyl monomer~such as tetrafluoroethylene and :; chlorotriluoroethylene and a perfluorovinyl monomer having an ion-exchange group such as sulfonic acid group, carboxylic acid group and phosphoric acid group or a reactive group which can be converted into the ion-exchange group. It is also possible to use a membrane made of a polymer of trifluoroethylene in which ion-exchange groups/ such as the sulfonic acid group are introduced or a polymer of styrene-divinyl benzene in which the sulfonic acid groups are introduced.
The cation exchange membrane is preferably made of a fluorinated polymer having the following units (M) ~ CF2-CXX'~ (M mole %) (N) ~ CF2- CX~ (N mole %) y wherein X represents fluorine, chlorine or hydrogen atom or -CF3;
X' represents X or CF3(CF2~ ; m represents an integer of 1 to 5.
The typical examples of Y have the structures bonding A
to a fluorocarbon group such as ~CF2~A, -O~CF~A, ~O-CF2- IcFty A, -CF2~O-CF2-CF~A, ~O-CF2-CF~ O-CF2-CF~A and Z Z Rf --CF2~CF-O-CF2 )X ( CF2 )y ( CF2 0 1 )z Z Rf x, y and z respectively represent an integer of 1 to 10; Z and Rf represent -F or a Cl - Clo perfluoroalkyl group; and ~7~9~L
A represents -COOM or -S03M, or a functional group which is : convertible into -COOM or -S03M by hydrolysis or neutralizationJ
h CN COF -COOR1, -S02F~ -CoNR2 3 2 2 3 J
and M represents hydrogen or an alkali metal atom; R1 represents a C1 - C10 alkyl group; R2 and R3 represent H or a C1 - C10 alkyl group.
It is preferable to use a fluorinated cation exchange mem-brane having a ion exchange group content of 0. 5 to aS. 0 especially 1. 0 to 20 meq/g. dry resin which is made of said copolymer, since the desired objects af the present invention are attained in a stable condition and high degree especially excellent clurability for a long time, In the preparation of such perfluoro polymer, one or more monomers for forming the units (M) and (N) can be used, if necessary, with a third m~>nomer so as to improve the mernhrane. For example, the flexibility can be imparted to the membrane by incorporating CF2 = CFOE~f (Rf is a Cl - C10 perfluoroalkyl group), or mechanical strength of the membrane can be improved by crosslinking the copoly-mer with a divinyl monomer such as CF2 = CF-CF= CF2 or CF2 = cFo(cF2)l-3 CF= CF2 The copolymerization of the fluorinated olefin monomer and the monomer having acarboxylic acid group or a functional group which is convertible into carboxylic acid group, and if necessary the other monomer can be carried out by any desired conventional process.
The polymerization maY be carried out if necessary, using a solvent~
such as halohydrocarbons/by catalytic polymerization, thermal polymerization or radiation-induced polymerization. Fabrication of the ion exchange membrane from the resulting copolymer is not ~7~91 eritieal, for example it may be effeeted by eonventional methods, sueh as a pre~s-moulding method, a roll-moulding method, an extrusion-moulding method, a solution spreading method, a dispersion mould ng method or a powder moulding method. The thiekness of the mernbrane is pre ferably 20 to 1000 mierons, espeeially 50 to 400 mierons.
When the functional groups of the eation exchange membrane are groups whieh are not carboxylie acid groups or sulfonic acid groups, but are convertible to carboxylic acid groups or sulfonie aeid groups sueh as -CNj -COF, -COOR1, -SO2FJ -CONR2R3, -SO2NR2R3 (R1 to R3 are defined above), the functional groups are eonverted to carboxylic acid groups or sulfonic acid groups by hydrolysis or neutralization with an acid or an alcoholic solution of a base or by reacting COF2 with double bonds as the funetional groups before the hydrolysis.
When the cation exchange membrane having carboxylic acid groups is used, the screen printing and bonding of the electrode - layer on the surface of the cation exchange membrane is preferably earried out under eonditions of the funetional groups having the formula -COOL (L represents hydrogen atom or a lower alkyl group) whereby the bonding of the electrode layer to the cation exchange membrane is especially improved in the heat-bonding whereby the electrolytie eell having exeellent eharaeteristics can be obtained.
The cation exchange membrane used in the present invention ean be fabricated by blending a polyolefin~such as polyethylene, polypropylene, preferably a fluorinated polymer such as polytetrafluoroethylene and a copolymer of ethylene and tetrafluoro-ethylene. The nembrane ean be reinforeed by supporting said copolymer on a fabric, such as a woven fabric or a net, a non-woven fabric or a porous film made of sald polymer or wires, a net or a perforated plate made of a metal. The weight of the polymers for the blend or the support is not considered in the measurement of the ion exchange capaclty.
In the preparation of an alkali metal hydroxide by the electrolysis of an aqueous solution of an alkali metal chloride in the electrolytic cell of the present invention, an aqueous solution of an alkali metal chloride is fed into the anode compartment partitioned by the cation exchange membrane and water is fed into the cathode compartment. Sodium chloride is usually used as the alkali metal chloride. It is also possible to use another alkali metal chloride, such as potassium ` chloride and lithium chloride. The corresponding alkali metal hydroxide can be produced from the aqueous solution at high efficiency and under stable conditions for a long period of time.
The electrolytic cell using the cation exchange membrane having the electrode layers may be a unipolar or bipolar type electrolytic cell. As a material for the electrolytic cell, a material which is resistant to an aqueous solution of an alkali metal chloride and chlorine, such as titanium is used for the anode compartment and a material which is resistant to an alkali metal hydroxide having high concentration and hydrogen, such as iron, stainless steel or nickel is used for the cathode compartment in the electrolysis of an alkali metal chloride. When the porous electrodes are used in the present invention, each current collector for feeding the current is placed outside each electrode. The current collectors usually have the same or 1~72~
higher overvoltage for chlorine or hydrogen in comparison with that of the electrodes. Eor example, the current collector at the anode side is made of a precious metal or a valve metal coated with a precious metal or oxide thereof and the current collector at the cathode side is made of nickel, stainless steel or expanded metal in a form of a mesh or a net. The current collectors are contacted with the porous electrodes under a pressure.
In the present invention, the process condition for the electrolysis of an aqueous solution of an alkali metal chloride may be conventional condi~ions in the prior arts such as those in British Patent 2,009,795. For example, an aqueous solution of an alkali metal chloride (2.5 to 5.0 Normal) is fed into the anode compartment and water or a dilute solution of an alkali metal hydroxide is fed into the cathode compartment and the electrolysis is preferably carried out at 80 to 120C
and at a current density of 10 to 100 A/dm .
The process for producing the alkali metal hydroxide and chlorine by the electrolysis of the aqueous solution of the alkali metal chloride has been illustrated. The present invention may also be used for the preparation of the cells for the electrolysis of water with the electrolysis of a desired alkali metal salt, such as sodium sulfate and a fuel cell.
The present invention will be further illustrated by the following Examples and References.
~1~7~Z91 EXAMPLE 1:
Into 95 wt.parts of water, 1 wt.parts of carboxymethyl cellulose (hereinafter referred to as CMC) and 5 wt, parts of poly-vinyl alcohol (hereinafter referred to as PVA) were dissolved at 80C
S to prepare a viscous solution. 35 wt. parts of 60 wt. % aaueous disper-sion of polytetrafluoroethylene (hereinafter referred to as PTFE) having a particle diameter of less than 1~U and 200 wt.parts of platinum black powder having a particle diameter of less than 25~ were added into the viscous solution and the mixture was kneaded to obtain paste 1.
Paste 1 was printed, in a size of 20 cm x 25 cm, by a screen printing process using a stainless steel screen having a mesh number of 200 and a thickness of 60~ and a printing plate with a screen mask having a thickness of 8~ and a polyurethane squeeze, on one sur-face of a cation exchange membrane having a cation exchange capacity of 1.45 meq/g. resin and a thickness of 250~/1 which is made of a copolymer of CF2=CF2 and CF2=CFO(CF2)3COOCH3. The printed layer on the cation exchange membrane was dried in air to solidify the paste as the anode. The resulting anode had a thickness of about 14~ and contained Pt at a ratio of 3 mg/cm .
The viscous solution was admixed with 35 wt. parts of 60 wt. % aqueous dispersion of PTFE having a particle diameter of less than 1~ and 200 wt. parts of stabilized Raney nickel powder having a particle diameter of less than 25,~ made by partial oxidizing Raney Ni particle after the dissolution aluminum with base so as to obtain Paste 2.
29~L
Paste 2 was printed~in a size of 20 cm x 25 cm~by a screen printing process using a stainless steel screen having a mesh number of 200 and a thickness of 80fl and a printing plate with a screen mask having a thickness of 30~Ll and a polyurethane squeez;e, on the other surface of the cation exchange membrane. The printed layer was dried in air to solidify the paste as the cathode. The resulting cathode had a thickness of 35,~ and contained Ni at a ratio of 7 mg/cm .
The printed layers were bonded to the cation exchange membrane at 150C under a pressure of 25 kg/cm . The product was dipped into 25% aqueous solution of sodium hydroxide at 90C for 16 hours to hydrolyze the cation exchange membrane and to remove CMC and PVA. A platinum mesh as a current collector was contacted with each of the cathode and the anode to form an eilectrolytic cell Electrolysis was carried out while maintaining 4 Normal of a concentration of sodium chloride in the anode compartment and ma inta ining 3 5 wt . % of a c oncentrat ion of s odium hydrox ide as the catholyte by feeding water into the cathode compartment.
The results are as follows.
20Current densityCell voltage (V) (A/dm2) 2. 65 2 . 87
electrode is non-uniform or a contact between the electrode with the cation exchange membrane is not satisfactory, a part of the electrode is easily peeled off whereby a cell voltage increases or the gas and the solution remain in the interfaces to cause the increase of the cell vo]tage. The desired advantages of the electrolytic cell are decreased or lost.
-2a-The present invention provides a cation exchange membrane type electrolytic cell having excellent character-istics which is formed by bonding electrodes having a uniforrr thickness to a cation exchange membrane without any gap by a novel means for bonding the gas-liquid permeable porous electrode to the cation exchange memhrane, In accordance wi th the present invention a cation exchange membrane type electrolytic cell i s provided which is formed by bonding each gas-liquid permeable porous electrode to a cation exchange membrane by a screen printing process using a paste comprising an electrode powder.
' .
In the screen printing process for bonding the electrode layer to the cation exchange membrane, a paste comprising an ele-trode powder is used.
`r~ The electrodes can be formed by any material for the anode and the cathode, The anode is preferably formed by one or more platinum group metal such as platinum, ruthenium, rhodium, and iridium and electroconductive oxides thereof, and electroconductive reduced oxides thereof. The cathode is preferably formed by one or more of iron, nickel, stainless steel, a thermally decomposed product of a fatty acid nickel salt, Raney nickel, stabilized Raney nickel, carbonyl nickel and carbon powder supporting a platinum group metal.
~7;291 ,:
The electrode powder is incorporated in the paste in the form of a powder having a particle diameter of 0. 01 to 300~ especially 0,1 to 100/~. A hydrophobic polymer is preferably incorporated in the paste. The hydrophobic polymer is used as a binder for the electrode and the cation exchange rnembrane, Suitable hydrophobic .' polymers include fluorocarbon polyrners ~such as polytetrafluoro-ethylene and polyhexylfluoroethylene. The hydrophobic polymer having a particle diameter of 0 1 to 500fc/especially 0. 1 to 100~ is preferably incorporated so as to be thoroughly dispersed in the paste. In order to improve the dispersibility, it is preferable to incorporate a long chain hydrocarbon type surfactant or a fluorinated hydrocarbon type surfactant at a desired ratio The contents of the electrode powder and the hydrophobic polymer in the paste depend upon the characteristics of the ele-ctrode. The former is preferably in a range of 20 to 95 wt. %/
especially 40 to 90 wt. %. The latter is preferably in a range of 0. 1 to 80 wt, %/ especially 1 to 60 wt. % The viscosity of the paste . comprising the electrode powder is preferably controlled in the range of 1 to 105 poises/especially 10 to 104 poises before the screen printing.
The viscosity can be controlled by selecting particle sizes and contents of the electrode powder and the hydrophobic polymer and the content of water as the medium and preferably controlled in said range by incorporatin~ a viscosity regulating agent, The viscosity regulating agents may be water soluble viscous materials which are gradually soluble in water. Suitable viscosity regulating agents include cellulose type materialsj such as carboxy-methyl cellulose, methyl cellulose, hydroxyethyl cellulose, and cellulose and polyethyleneglycol polyvinyl alcohol, polyvinyl pyrro-lidone, sodium polyacrylate and polymethyl vinyl ether.
11~7~
The properties of the electrode do not deteriorate by the in-corporation of the viscosity regulating agent because of its ; water solubility. It is also possible to use any material which does not deteriorate the electrolytic characteristics by re-action or corrosion of the electrode layer in the preparation and the use of the electrode layer, such as casein and poly-acrylamide.
The paste is printed on and bonded to the surface of the cation exchange membrane by the screen printing process.
The conventional screen printing process can be employed. It is preferable to use a screen having a mesh number of 10 to 2400, especially a mesh number of 150 to 1000 and a thickness of 2 mm to 4~ , especially 300~ to 8~ hen the mesh is too large, clog-ging of the screen occurs with non-uniform printing. When the mesh is too small, excess of the paste is printed. When the thickness is too thick, non-: uniform printing is caused. When the thickness is too small, printing for a desired amount of paste is not attained. A screen mask is used for forming the electrode layer having a desired size and configuration on the - surface of the cation exchange membrane. The configuration is preferably a printed pattern eliminating the configuration of the electrode. The thickness of screen mask is preferably in the range of 1 to 500~ . The substances for the screen and the screen mask can be any materials having satisfactory strength such as stainless steel, polyethyleneterephthalate and nylon for the screen and epoxy resins for the screen mask.
A screen and the screen mask are placed on the cation exchange membrane for the printing of the electrode layer. The paste is fed on the screen and is printed under a desired pressure by squeezing whereby the electrode layer having the configuration determined by the screen mask is formed on the surface of the cation exchange membrane. The thickness of the electrode layer on the cation exchange membrane depends upon the 7~9~l thickness of the screen, the viscosity of the paste and the mesh number of the screen. It is preferable to control the thickness of the screen, the viscosity of the paste and the mesh of the screen so as to give the thickness of the electrode ranging from 0.1 to 100~, especially 1 to 50~.
; The gap between the screen and the cation exchange membrane and the material being squeezed and the pressure applied to mesh by the squeezing in the screen printing process greatly determine the physical properties, thickness and uniformity of o the electrode layer formed on the surface of the cation exchange membrane. In order to give desired printing, the gap between the screen and the cation exchange membrane is set depending upon the type and viscosity of the paste, preferably ranging from 0.5 mm to 5 cm, and the hardness of the squeeze having a sharp corner is selected according to the viscosity of the paste, -~ preferably ranging from 50 to 100 shore hardness, and the uni-form pressure of the squeeze is applied to the mesh. Thus the electrode layer having uniform thickness is formed on one or both of the surfaces of the cation exchange membrane at a high bonding strength. Thereafter it is preferable to press the electrode layer on the surface of the cation exchange membrane at 100 to 300C, and especially 110 to 250~C under a pressure of 5 to 1000 kg/cm2 and especially 20 to 500 kg/cm2 whereby a strongly bonded structure of the electrode layer and the cation exchange membrane can be obtained.
The electrode layer formed on the cation exchange membrane should be a gas permeable porous layer. The average pore diameter is preferably in the range of 0.01 to 50 ~, especially 0.1 to 30f~. The porosity is preferably in the range of 10 to 99%, especially 20 to 95%. The thickness is preferably in the range of 0.1 to 100/~-, especially 1 to 50~.
The cation exchange membrane on which the electrode 1~47~9iL
layer is formed may be made of a polymer having cation exchange groups such as carboxylic acid groups, sulfonic acid groups, - 6a -7'~1 ,, phosphoric acid groups and phenolic hydroxy groups. Suitable polymers include copolymers of a vinyl monomer~such as tetrafluoroethylene and :; chlorotriluoroethylene and a perfluorovinyl monomer having an ion-exchange group such as sulfonic acid group, carboxylic acid group and phosphoric acid group or a reactive group which can be converted into the ion-exchange group. It is also possible to use a membrane made of a polymer of trifluoroethylene in which ion-exchange groups/ such as the sulfonic acid group are introduced or a polymer of styrene-divinyl benzene in which the sulfonic acid groups are introduced.
The cation exchange membrane is preferably made of a fluorinated polymer having the following units (M) ~ CF2-CXX'~ (M mole %) (N) ~ CF2- CX~ (N mole %) y wherein X represents fluorine, chlorine or hydrogen atom or -CF3;
X' represents X or CF3(CF2~ ; m represents an integer of 1 to 5.
The typical examples of Y have the structures bonding A
to a fluorocarbon group such as ~CF2~A, -O~CF~A, ~O-CF2- IcFty A, -CF2~O-CF2-CF~A, ~O-CF2-CF~ O-CF2-CF~A and Z Z Rf --CF2~CF-O-CF2 )X ( CF2 )y ( CF2 0 1 )z Z Rf x, y and z respectively represent an integer of 1 to 10; Z and Rf represent -F or a Cl - Clo perfluoroalkyl group; and ~7~9~L
A represents -COOM or -S03M, or a functional group which is : convertible into -COOM or -S03M by hydrolysis or neutralizationJ
h CN COF -COOR1, -S02F~ -CoNR2 3 2 2 3 J
and M represents hydrogen or an alkali metal atom; R1 represents a C1 - C10 alkyl group; R2 and R3 represent H or a C1 - C10 alkyl group.
It is preferable to use a fluorinated cation exchange mem-brane having a ion exchange group content of 0. 5 to aS. 0 especially 1. 0 to 20 meq/g. dry resin which is made of said copolymer, since the desired objects af the present invention are attained in a stable condition and high degree especially excellent clurability for a long time, In the preparation of such perfluoro polymer, one or more monomers for forming the units (M) and (N) can be used, if necessary, with a third m~>nomer so as to improve the mernhrane. For example, the flexibility can be imparted to the membrane by incorporating CF2 = CFOE~f (Rf is a Cl - C10 perfluoroalkyl group), or mechanical strength of the membrane can be improved by crosslinking the copoly-mer with a divinyl monomer such as CF2 = CF-CF= CF2 or CF2 = cFo(cF2)l-3 CF= CF2 The copolymerization of the fluorinated olefin monomer and the monomer having acarboxylic acid group or a functional group which is convertible into carboxylic acid group, and if necessary the other monomer can be carried out by any desired conventional process.
The polymerization maY be carried out if necessary, using a solvent~
such as halohydrocarbons/by catalytic polymerization, thermal polymerization or radiation-induced polymerization. Fabrication of the ion exchange membrane from the resulting copolymer is not ~7~91 eritieal, for example it may be effeeted by eonventional methods, sueh as a pre~s-moulding method, a roll-moulding method, an extrusion-moulding method, a solution spreading method, a dispersion mould ng method or a powder moulding method. The thiekness of the mernbrane is pre ferably 20 to 1000 mierons, espeeially 50 to 400 mierons.
When the functional groups of the eation exchange membrane are groups whieh are not carboxylie acid groups or sulfonic acid groups, but are convertible to carboxylic acid groups or sulfonie aeid groups sueh as -CNj -COF, -COOR1, -SO2FJ -CONR2R3, -SO2NR2R3 (R1 to R3 are defined above), the functional groups are eonverted to carboxylic acid groups or sulfonic acid groups by hydrolysis or neutralization with an acid or an alcoholic solution of a base or by reacting COF2 with double bonds as the funetional groups before the hydrolysis.
When the cation exchange membrane having carboxylic acid groups is used, the screen printing and bonding of the electrode - layer on the surface of the cation exchange membrane is preferably earried out under eonditions of the funetional groups having the formula -COOL (L represents hydrogen atom or a lower alkyl group) whereby the bonding of the electrode layer to the cation exchange membrane is especially improved in the heat-bonding whereby the electrolytie eell having exeellent eharaeteristics can be obtained.
The cation exchange membrane used in the present invention ean be fabricated by blending a polyolefin~such as polyethylene, polypropylene, preferably a fluorinated polymer such as polytetrafluoroethylene and a copolymer of ethylene and tetrafluoro-ethylene. The nembrane ean be reinforeed by supporting said copolymer on a fabric, such as a woven fabric or a net, a non-woven fabric or a porous film made of sald polymer or wires, a net or a perforated plate made of a metal. The weight of the polymers for the blend or the support is not considered in the measurement of the ion exchange capaclty.
In the preparation of an alkali metal hydroxide by the electrolysis of an aqueous solution of an alkali metal chloride in the electrolytic cell of the present invention, an aqueous solution of an alkali metal chloride is fed into the anode compartment partitioned by the cation exchange membrane and water is fed into the cathode compartment. Sodium chloride is usually used as the alkali metal chloride. It is also possible to use another alkali metal chloride, such as potassium ` chloride and lithium chloride. The corresponding alkali metal hydroxide can be produced from the aqueous solution at high efficiency and under stable conditions for a long period of time.
The electrolytic cell using the cation exchange membrane having the electrode layers may be a unipolar or bipolar type electrolytic cell. As a material for the electrolytic cell, a material which is resistant to an aqueous solution of an alkali metal chloride and chlorine, such as titanium is used for the anode compartment and a material which is resistant to an alkali metal hydroxide having high concentration and hydrogen, such as iron, stainless steel or nickel is used for the cathode compartment in the electrolysis of an alkali metal chloride. When the porous electrodes are used in the present invention, each current collector for feeding the current is placed outside each electrode. The current collectors usually have the same or 1~72~
higher overvoltage for chlorine or hydrogen in comparison with that of the electrodes. Eor example, the current collector at the anode side is made of a precious metal or a valve metal coated with a precious metal or oxide thereof and the current collector at the cathode side is made of nickel, stainless steel or expanded metal in a form of a mesh or a net. The current collectors are contacted with the porous electrodes under a pressure.
In the present invention, the process condition for the electrolysis of an aqueous solution of an alkali metal chloride may be conventional condi~ions in the prior arts such as those in British Patent 2,009,795. For example, an aqueous solution of an alkali metal chloride (2.5 to 5.0 Normal) is fed into the anode compartment and water or a dilute solution of an alkali metal hydroxide is fed into the cathode compartment and the electrolysis is preferably carried out at 80 to 120C
and at a current density of 10 to 100 A/dm .
The process for producing the alkali metal hydroxide and chlorine by the electrolysis of the aqueous solution of the alkali metal chloride has been illustrated. The present invention may also be used for the preparation of the cells for the electrolysis of water with the electrolysis of a desired alkali metal salt, such as sodium sulfate and a fuel cell.
The present invention will be further illustrated by the following Examples and References.
~1~7~Z91 EXAMPLE 1:
Into 95 wt.parts of water, 1 wt.parts of carboxymethyl cellulose (hereinafter referred to as CMC) and 5 wt, parts of poly-vinyl alcohol (hereinafter referred to as PVA) were dissolved at 80C
S to prepare a viscous solution. 35 wt. parts of 60 wt. % aaueous disper-sion of polytetrafluoroethylene (hereinafter referred to as PTFE) having a particle diameter of less than 1~U and 200 wt.parts of platinum black powder having a particle diameter of less than 25~ were added into the viscous solution and the mixture was kneaded to obtain paste 1.
Paste 1 was printed, in a size of 20 cm x 25 cm, by a screen printing process using a stainless steel screen having a mesh number of 200 and a thickness of 60~ and a printing plate with a screen mask having a thickness of 8~ and a polyurethane squeeze, on one sur-face of a cation exchange membrane having a cation exchange capacity of 1.45 meq/g. resin and a thickness of 250~/1 which is made of a copolymer of CF2=CF2 and CF2=CFO(CF2)3COOCH3. The printed layer on the cation exchange membrane was dried in air to solidify the paste as the anode. The resulting anode had a thickness of about 14~ and contained Pt at a ratio of 3 mg/cm .
The viscous solution was admixed with 35 wt. parts of 60 wt. % aqueous dispersion of PTFE having a particle diameter of less than 1~ and 200 wt. parts of stabilized Raney nickel powder having a particle diameter of less than 25,~ made by partial oxidizing Raney Ni particle after the dissolution aluminum with base so as to obtain Paste 2.
29~L
Paste 2 was printed~in a size of 20 cm x 25 cm~by a screen printing process using a stainless steel screen having a mesh number of 200 and a thickness of 80fl and a printing plate with a screen mask having a thickness of 30~Ll and a polyurethane squeez;e, on the other surface of the cation exchange membrane. The printed layer was dried in air to solidify the paste as the cathode. The resulting cathode had a thickness of 35,~ and contained Ni at a ratio of 7 mg/cm .
The printed layers were bonded to the cation exchange membrane at 150C under a pressure of 25 kg/cm . The product was dipped into 25% aqueous solution of sodium hydroxide at 90C for 16 hours to hydrolyze the cation exchange membrane and to remove CMC and PVA. A platinum mesh as a current collector was contacted with each of the cathode and the anode to form an eilectrolytic cell Electrolysis was carried out while maintaining 4 Normal of a concentration of sodium chloride in the anode compartment and ma inta ining 3 5 wt . % of a c oncentrat ion of s odium hydrox ide as the catholyte by feeding water into the cathode compartment.
The results are as follows.
20Current densityCell voltage (V) (A/dm2) 2. 65 2 . 87
3. 05 ' 40 3.19 The current efficiency for producing sodium hydroxide at a current density of 20 A/dm2 was 95%. When the electrolysis at 20 A/dm2 was continued for one month, the cell voltage was substantial-ly constant and no peeling-off of the electrodes from the cation exchange membrane was found.
11~7291 EXAMPLE 2:
.
In accordance with the process of Example 1 except using a viscous solution produced by dissolving 1 wt. part of CMC in 50 wt.
parts of ethylene glycol at 100C, electrodes were bonded to the cation exchange membrane, and the electrolysis was carried out in the same condition. The results are as follows.
Current densityCell voltage (V) (A/dm2) 2 . 67 2. 89 3 . 0 7 3 , 2 1 The current efficiency for producing sodium hydroxide at a current density of 20 A/dm2 was 94%.
In accordance with the process of Example 1 except using a viscous solution produced by dissolving 10 wt. parts of PVA and 20 wt. parts of polyvinylpyrrolidone in lO0 wt. parts of water at 80C, electrodes were bonded to the cation exchange membrane and the electrolysis was carried out in the same condition. The results are as follows.
Current densityCell voltage (V) (A/dm2) 2. 68 2. 92 3.07 3. 22 ~7~91 The current efficiency for producing sodium hydroxide at a current density of 20 ~/dm was 94%.
EXAMPLE 4:
-In accordance with the process of Example 1 except using a mixture of platinum black powder and iridium black powder (atomic ratio of 70: 30) having a particle diameter of less than 25~r~ instead of platinum black powder in the anode, electrodes were bonded to the cation exchange membrane and the electrolysis was carried out in the same condition. The results are as follows.
10Current density Cell voltage (A/dm2) (V) 2.66 2, 89 3.06 3.20 The current efficiency for producing sodium hydroxide at a current density of 20 A/dm2 was 94%.
7~91 .
EXAMPLE 5:
In accordance with the process of Example 1 except using a stainless steel scrren printing plate having a mesh of 400 and a thickness of 52~ to print on the cation exchange membrane by the screen printing, electrodes were bonded to the cation exchange membrane. The anode had a thickness of about 9~ and contained platinum at a ratio of 2 mg!cm .
In accordance with the process of Example 1, the electrolysis was carried out in the same condition. The results are as follows.
~: 10Current d2ensity Cell voltage (A/dm ) (V) 2. 67 2, 90 3. 07 3, 21 The current efficiency for producing sodium hydrate at a current density of 20 A/dm was 94%.
47~91 EXAMPLE 6:
In accordance with the process of Example 1 except using the following pastes for the anode and the cathode, electrodes were bonded to the cation exchange membrane.
The paste for the anode was prepared by kneading the mixture of 70 wt.parts of platinum black powder having a particle diameter of less than 25~ and 30 wt, parts of 20 wt. % aqueous dispersion of PTFE
having a particle diameter of less than 25~
The paste `for the cathode was prepared by kneading the mixture of 75 wt. parts of stabili~ed Raney nickel having a particle diameter of less than 25~ and 25 wt.parts of 30 wt. % aqueous disper-sion of PTFE having a particle diameter of less than 1~
; In accordance with the process of Example 1, the electrolysis was carried out in the same condition. The results are as follows.
15Current density Cell voltage (A/dm2) (V) 2.64 2 . 85 3 0 3 . 0 3 3. 17 The current efficiency for producing sodium hydroxide at a current density of 20 A/dm was 95%.
~1~7;~91 EXAMPLE 7:
In accordance with the process of Example l except that polytetrafluoroethylene having a particle diameter of less than l~L was not incorporated in the paste, electrodes were bonded to the cation exchange membrane and the electrolysis was carried out in the same condition. The results are as follows.
Current density Cell voltage (A/dm2) (V) l O 2 . 64 2.85 3 . 03 3. l 6 The current efficiency for producing sodium hydrate at a current density of 20 A/dm was 93%, ~7~91.
EXAMP LE 8:
In accordance with the process of Example 1 except using a cation exchange membrane made of a copolymer of CF2=CF2 and CF2=cFocF2cF(cF3)ocF2cF2so2F (ion exchange capacity of 0. 87 meq/g. dry resin and thickness of 300,~L), electrodes were bonded to the cation exchange membrane and the electrolysis was carried out - in the same condition. The results are as follows.
Current density Cell voltage (A/dm2) (V) 10 10 2, 75 3.00 3.21 3 . 3 5 The current efficiency for producing sodium hydrate at a 15current density of 20 A/dm2 was 84%.
. .
11~7291 EXAMPLE 2:
.
In accordance with the process of Example 1 except using a viscous solution produced by dissolving 1 wt. part of CMC in 50 wt.
parts of ethylene glycol at 100C, electrodes were bonded to the cation exchange membrane, and the electrolysis was carried out in the same condition. The results are as follows.
Current densityCell voltage (V) (A/dm2) 2 . 67 2. 89 3 . 0 7 3 , 2 1 The current efficiency for producing sodium hydroxide at a current density of 20 A/dm2 was 94%.
In accordance with the process of Example 1 except using a viscous solution produced by dissolving 10 wt. parts of PVA and 20 wt. parts of polyvinylpyrrolidone in lO0 wt. parts of water at 80C, electrodes were bonded to the cation exchange membrane and the electrolysis was carried out in the same condition. The results are as follows.
Current densityCell voltage (V) (A/dm2) 2. 68 2. 92 3.07 3. 22 ~7~91 The current efficiency for producing sodium hydroxide at a current density of 20 ~/dm was 94%.
EXAMPLE 4:
-In accordance with the process of Example 1 except using a mixture of platinum black powder and iridium black powder (atomic ratio of 70: 30) having a particle diameter of less than 25~r~ instead of platinum black powder in the anode, electrodes were bonded to the cation exchange membrane and the electrolysis was carried out in the same condition. The results are as follows.
10Current density Cell voltage (A/dm2) (V) 2.66 2, 89 3.06 3.20 The current efficiency for producing sodium hydroxide at a current density of 20 A/dm2 was 94%.
7~91 .
EXAMPLE 5:
In accordance with the process of Example 1 except using a stainless steel scrren printing plate having a mesh of 400 and a thickness of 52~ to print on the cation exchange membrane by the screen printing, electrodes were bonded to the cation exchange membrane. The anode had a thickness of about 9~ and contained platinum at a ratio of 2 mg!cm .
In accordance with the process of Example 1, the electrolysis was carried out in the same condition. The results are as follows.
~: 10Current d2ensity Cell voltage (A/dm ) (V) 2. 67 2, 90 3. 07 3, 21 The current efficiency for producing sodium hydrate at a current density of 20 A/dm was 94%.
47~91 EXAMPLE 6:
In accordance with the process of Example 1 except using the following pastes for the anode and the cathode, electrodes were bonded to the cation exchange membrane.
The paste for the anode was prepared by kneading the mixture of 70 wt.parts of platinum black powder having a particle diameter of less than 25~ and 30 wt, parts of 20 wt. % aqueous dispersion of PTFE
having a particle diameter of less than 25~
The paste `for the cathode was prepared by kneading the mixture of 75 wt. parts of stabili~ed Raney nickel having a particle diameter of less than 25~ and 25 wt.parts of 30 wt. % aqueous disper-sion of PTFE having a particle diameter of less than 1~
; In accordance with the process of Example 1, the electrolysis was carried out in the same condition. The results are as follows.
15Current density Cell voltage (A/dm2) (V) 2.64 2 . 85 3 0 3 . 0 3 3. 17 The current efficiency for producing sodium hydroxide at a current density of 20 A/dm was 95%.
~1~7;~91 EXAMPLE 7:
In accordance with the process of Example l except that polytetrafluoroethylene having a particle diameter of less than l~L was not incorporated in the paste, electrodes were bonded to the cation exchange membrane and the electrolysis was carried out in the same condition. The results are as follows.
Current density Cell voltage (A/dm2) (V) l O 2 . 64 2.85 3 . 03 3. l 6 The current efficiency for producing sodium hydrate at a current density of 20 A/dm was 93%, ~7~91.
EXAMP LE 8:
In accordance with the process of Example 1 except using a cation exchange membrane made of a copolymer of CF2=CF2 and CF2=cFocF2cF(cF3)ocF2cF2so2F (ion exchange capacity of 0. 87 meq/g. dry resin and thickness of 300,~L), electrodes were bonded to the cation exchange membrane and the electrolysis was carried out - in the same condition. The results are as follows.
Current density Cell voltage (A/dm2) (V) 10 10 2, 75 3.00 3.21 3 . 3 5 The current efficiency for producing sodium hydrate at a 15current density of 20 A/dm2 was 84%.
. .
Claims (8)
1. An electrolytic cell having a gas-liquid perme-able porous electrode layer on a cation exchange membrane, wherein said electrode layer is formed by screen printing a paste comprising a hydrophobic polymer and an electrode powder on the surface of said cation exchange membrane, wherein said electrode powder is a metal, an electroconductive metal oxide, or an electroconductive reduced metal oxide powder, and bonding said paste to said membrane by the application of heat and pressure.
2. The electrolytic cell according to claim 1 wherein said electrode layer is an anode and said electrode powder for said anode is made of a platinum group metal or an electric conductive oxide thereof or an electric conductive reduced oxide thereof.
3. The electrolytic cell according to claim 1 wherein said electrode layer is a cathode and said electrode powder for said cathode is made of a platinum group metal or an electric conductive oxide thereof or an iron group metal.
4. The electrolytic cell according to claim 1 wherein said electrode layer has a porosity of 10 to 99% and a thickness of 0.1 to 100µ.
5. The electrolytic cell according to claim 1 or 3 wherein said screen has a mesh number of 10 to 2400 and a thicnkess of 2mm to 4µ.
6. The electrolytic cell according to claim 1, 3 or 4 wherein said cation exchange membrane is made of a fluori-nated polymer having carboxylic acid groups or sulfonic acid groups.
7. The electrolytic cell according to claim 1 wherein said cation exchange membrane is made of a copolymer having the units (M) (M mole %) (N) (N mole %) wherein X represents fluorine, chlorine,or hydrogen atom or - CF3; X' represents X or CF3 ; m represents an integer of 1 to 5; Y represents the following unit;
, , , , , and x, y and z respectively represent an integer of 1 to 10; Z and Rf represent - F or C1-C10 perfluoroalkyl group; and A repre-sents - COOM or - SO3M or a functional group which is convert-ible into - COOM or - SO3M by a hydrolysis or a neutralization such as -CN, -COF, -COORl, -SO2F, CONR2R3 and -SO2NR2R3 and M represents hydrogen or an alkali metal atom; Rl represents a Cl-C10 alkyl group; R2 and R3 represent H or a Cl-C10 alkyl group.
, , , , , and x, y and z respectively represent an integer of 1 to 10; Z and Rf represent - F or C1-C10 perfluoroalkyl group; and A repre-sents - COOM or - SO3M or a functional group which is convert-ible into - COOM or - SO3M by a hydrolysis or a neutralization such as -CN, -COF, -COORl, -SO2F, CONR2R3 and -SO2NR2R3 and M represents hydrogen or an alkali metal atom; Rl represents a Cl-C10 alkyl group; R2 and R3 represent H or a Cl-C10 alkyl group.
8. The electrolytic cell according to claim 1, which is used for producing an alkali metal hydroxide and chlorine by an electrolysis of an aqueous solution of an alkali metal chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54110234A JPS5827352B2 (en) | 1979-08-31 | 1979-08-31 | Manufacturing method of ion exchange membrane with electrode layer attached |
| JP110234/1979 | 1979-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1147291A true CA1147291A (en) | 1983-05-31 |
Family
ID=14530489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000359278A Expired CA1147291A (en) | 1979-08-31 | 1980-08-29 | Ion exchange membrane type electrolytic cell |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4319969A (en) |
| EP (1) | EP0026979B1 (en) |
| JP (1) | JPS5827352B2 (en) |
| CA (1) | CA1147291A (en) |
| DE (1) | DE3066183D1 (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU535261B2 (en) * | 1979-11-27 | 1984-03-08 | Asahi Glass Company Limited | Ion exchange membrane cell |
| FI72150C (en) * | 1980-11-15 | 1987-04-13 | Asahi Glass Co Ltd | Alkalimetallkloridelektrolyscell. |
| US4496451A (en) * | 1981-05-22 | 1985-01-29 | Asahi Glass Company, Ltd. | Ion exchange membrane manufacture for electrolytic cell |
| US4421579A (en) * | 1981-06-26 | 1983-12-20 | Diamond Shamrock Corporation | Method of making solid polymer electrolytes and electrode bonded with hydrophyllic fluorocopolymers |
| EP0120212B1 (en) * | 1983-02-25 | 1986-10-01 | BBC Aktiengesellschaft Brown, Boveri & Cie. | Process for producing an electrically conductive layer on a solid electrolyte surface, and electrically conductive layer |
| US4871703A (en) * | 1983-05-31 | 1989-10-03 | The Dow Chemical Company | Process for preparation of an electrocatalyst |
| US4510026A (en) * | 1983-11-16 | 1985-04-09 | Panclor S.A. | Process for electrolysis of sea water |
| JPS61133548U (en) * | 1985-02-09 | 1986-08-20 | ||
| US4826554A (en) * | 1985-12-09 | 1989-05-02 | The Dow Chemical Company | Method for making an improved solid polymer electrolyte electrode using a binder |
| US4654104A (en) * | 1985-12-09 | 1987-03-31 | The Dow Chemical Company | Method for making an improved solid polymer electrolyte electrode using a fluorocarbon membrane in a thermoplastic state |
| US4889577A (en) * | 1986-12-19 | 1989-12-26 | The Dow Chemical Company | Method for making an improved supported membrane/electrode structure combination wherein catalytically active particles are coated onto the membrane |
| US4752370A (en) * | 1986-12-19 | 1988-06-21 | The Dow Chemical Company | Supported membrane/electrode structure combination wherein catalytically active particles are coated onto the membrane |
| US4738741A (en) * | 1986-12-19 | 1988-04-19 | The Dow Chemical Company | Method for forming an improved membrane/electrode combination having interconnected roadways of catalytically active particles |
| US5039389A (en) * | 1986-12-19 | 1991-08-13 | The Dow Chemical Company | Membrane/electrode combination having interconnected roadways of catalytically active particles |
| AU582059B2 (en) * | 1986-12-19 | 1989-03-09 | Dow Chemical Company, The | A composite membrane/electrode structure having islands of catalytically active particles |
| US5415888A (en) * | 1993-04-26 | 1995-05-16 | E. I. Du Pont De Nemours And Company | Method of imprinting catalytically active particles on membrane |
| US5330860A (en) * | 1993-04-26 | 1994-07-19 | E. I. Du Pont De Nemours And Company | Membrane and electrode structure |
| DE4327254A1 (en) * | 1993-08-13 | 1995-02-16 | Mannesmann Ag | Process for the production of catalytically active gas diffusion electrodes |
| GB9324101D0 (en) * | 1993-11-23 | 1994-01-12 | Johnson Matthey Plc | Improved manufacture of electrodes |
| US5470448A (en) * | 1994-01-28 | 1995-11-28 | United Technologies Corporation | High performance electrolytic cell electrode/membrane structures and a process for preparing such electrode structures |
| AUPM506894A0 (en) * | 1994-04-14 | 1994-05-05 | Memtec Limited | Novel electrochemical cells |
| GB9504713D0 (en) * | 1995-03-09 | 1995-04-26 | Johnson Matthey Plc | Improved electrocatalytic material |
| US6413410B1 (en) * | 1996-06-19 | 2002-07-02 | Lifescan, Inc. | Electrochemical cell |
| US6638415B1 (en) | 1995-11-16 | 2003-10-28 | Lifescan, Inc. | Antioxidant sensor |
| US6863801B2 (en) * | 1995-11-16 | 2005-03-08 | Lifescan, Inc. | Electrochemical cell |
| AUPN661995A0 (en) | 1995-11-16 | 1995-12-07 | Memtec America Corporation | Electrochemical cell 2 |
| US6632349B1 (en) * | 1996-11-15 | 2003-10-14 | Lifescan, Inc. | Hemoglobin sensor |
| AUPO855897A0 (en) | 1997-08-13 | 1997-09-04 | Usf Filtration And Separations Group Inc. | Automatic analysing apparatus II |
| US6878251B2 (en) * | 1998-03-12 | 2005-04-12 | Lifescan, Inc. | Heated electrochemical cell |
| US6475360B1 (en) | 1998-03-12 | 2002-11-05 | Lifescan, Inc. | Heated electrochemical cell |
| RU2278612C2 (en) * | 2000-07-14 | 2006-06-27 | Лайфскен, Инк. | Immune sensor |
| US6444115B1 (en) | 2000-07-14 | 2002-09-03 | Lifescan, Inc. | Electrochemical method for measuring chemical reaction rates |
| DE10037074A1 (en) | 2000-07-29 | 2002-02-14 | Omg Ag & Co Kg | Ink for the production of membrane electrode assemblies for PEM fuel cells |
| RU2297696C2 (en) * | 2001-10-10 | 2007-04-20 | Лайфскен, Инк. | Electrochemical cell |
| US20030180814A1 (en) * | 2002-03-21 | 2003-09-25 | Alastair Hodges | Direct immunosensor assay |
| US20060134713A1 (en) * | 2002-03-21 | 2006-06-22 | Lifescan, Inc. | Biosensor apparatus and methods of use |
| CN114335639A (en) * | 2021-12-31 | 2022-04-12 | 苏州华清京昆新能源科技有限公司 | Method for preparing electrolyte film of solid oxide fuel cell with uniform compactness |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049844A (en) * | 1974-09-27 | 1977-09-20 | General Electric Company | Method for making a circuit board and article made thereby |
| US4001042A (en) * | 1975-09-02 | 1977-01-04 | United Technologies Corporation | Screen printing fuel cell electrolyte matrices using polyethylene oxide as the inking vehicle |
| US4039409A (en) * | 1975-12-04 | 1977-08-02 | General Electric Company | Method for gas generation utilizing platinum metal electrocatalyst containing 5 to 60% ruthenium |
| US4126588A (en) * | 1975-12-30 | 1978-11-21 | Asahi Glass Company Ltd. | Fluorinated cation exchange membrane and use thereof in electrolysis of alkali metal halide |
| US4101395A (en) * | 1976-08-30 | 1978-07-18 | Tokuyama Soda Kabushiki Kaisha | Cathode-structure for electrolysis |
| DE2741956A1 (en) * | 1976-09-20 | 1978-03-23 | Gen Electric | ELECTROLYSIS OF SODIUM SULFATE USING AN ION EXCHANGE MEMBRANE CELL WITH SOLID ELECTROLYTE |
| JPS53144481A (en) * | 1977-05-24 | 1978-12-15 | Asahi Glass Co Ltd | Method of joining fluorine contained cation exchange resin membrane |
| US4224121A (en) * | 1978-07-06 | 1980-09-23 | General Electric Company | Production of halogens by electrolysis of alkali metal halides in an electrolysis cell having catalytic electrodes bonded to the surface of a solid polymer electrolyte membrane |
| DE2844496C2 (en) * | 1977-12-09 | 1982-12-30 | General Electric Co., Schenectady, N.Y. | Process for producing halogen and alkali metal hydroxides |
| US4185131A (en) * | 1978-06-28 | 1980-01-22 | United Technologies Corporation | Screen printing method for making an electrochemical cell electrode |
| US4229490A (en) * | 1978-09-01 | 1980-10-21 | Texas Instruments Incorporated | Novel method for catalyst application to a substrate for fuel cell electrodes |
| JPS5620178A (en) * | 1979-07-30 | 1981-02-25 | Asahi Glass Co Ltd | Closely sticking method for ion exchange membrane and electrode |
-
1979
- 1979-08-31 JP JP54110234A patent/JPS5827352B2/en not_active Expired
-
1980
- 1980-08-14 US US06/177,896 patent/US4319969A/en not_active Expired - Lifetime
- 1980-08-29 DE DE8080303028T patent/DE3066183D1/en not_active Expired
- 1980-08-29 EP EP80303028A patent/EP0026979B1/en not_active Expired
- 1980-08-29 CA CA000359278A patent/CA1147291A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3066183D1 (en) | 1984-02-23 |
| EP0026979B1 (en) | 1984-01-18 |
| EP0026979A2 (en) | 1981-04-15 |
| JPS5635785A (en) | 1981-04-08 |
| EP0026979A3 (en) | 1981-09-02 |
| US4319969A (en) | 1982-03-16 |
| JPS5827352B2 (en) | 1983-06-08 |
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