Separator membranes for electrochemical cells

Abstract

This disclosure is directed to polymer membranes to be used in electrochemical cells and improved processes for producing the same. The membranes are produced by radiation grafting techniques. The improved process includes the grafting of a hydrophilic monomer, such as methacrylic acid in a chlorinated organic solvent onto an inert base film such as polyethylene. The process also includes but is not limited to the use of inhibitors to limit homopolymerization of a grafting material, as well as emulsifying agents to lower the electrolytic resistance of the finished membrane.

What is claimed is: 
     
       1. An improved process for the preparation of a membrane suitable for use in electrochemical cells comprising: (a) forming a grafting solution comprising a hydrophilic monomer, and .[.an organic.]. .Iadd.a .Iaddend.solvent .Iadd.selected from the group consisting of an organic solvent which incorporates a transfer agent, and a chlorinated hydrocarbon; .Iaddend.   (b) placing said solution in contact with an inert polymeric film;   (c) irradiating said contacted film to graft polymerize said hydrophilic monomer onto the film, while inhibiting homopolymerization of said graft monomer; and   (d) contacting said irradiation grafted film with an emulsifier to reduce the electrolytic resistance of said membrane.   
     
     
       2. The process of claim 1 wherein the grafted polymeric film is laminated with at least one layer of cellophane. 
     
     
       3. The process of claim 1 wherein said grafting solution comprises from about 1 to 50% of said monomer, and from about 50 to 99% .Iadd.of a .Iaddend.chlorinated organic solvent by weight and said inert polymeric film is non-cross linked. 
     
     
       4. The process of claim 3 wherein said monomer is selected from the group of acrylic and methacrylic acid, said chlorinated organic solvent is methylene chloride. 
     
     
       5. The process of claim 4 wherein the hydrophilic monomer comprises about 20% and said organic solvent comprises about 80% of said grafting solution. 
     
     
       6. The process of claim 1 wherein said grafting solution comprises from about 10 to 50% of the monomer, from about 3 to 6% of a transfer agent and from about 44 to 87% of a solvent for said monomer each by weight of the entire grafting solution. 
     
     
       7. The process of claim 6 wherein said monomer is selected from the group of acrylic and methacrylic acid, said transfer agent is carbon tetrachloride and said solvent is toluene. 
     
     
       8. The process of claim 7 wherein said monomer is about 32%, said transfer agent is about 3.6% and said solvent is about 64.4% each by weight of the entire grafting solution. 
     
     
       9. The process of claim 1 wherein said emulsifier is a surface active agent selected from the group of anionics, cationics and non-ionics. 
     
     
       10. The process of claim 1 wherein a chemical inhibitor selected from the group of hydroquinone and hydroquinone methyl ether is added to the grafting solution to inhibit homopolymerization of the hydrophilic monomer. 
     
     
       11. The method of claim 10 wherein the chemical inhibitor is contained in a micro-porous polypropylene sack. 
     
     
       12. The process of claim 1 wherein air is introduced into the grafting solution to inhibit homopolymerization of the hydrophilic monomer. 
     
     
       13. The process of claim 11 wherein air is introduced to the lower portions of the grafting solution by means of a tube which extends from the lower portions of the grafting solution to a point outside said solution in contact with the atmosphere adapted at its lower end with a gas-permeable membrane which permits air to diffuse into the solution while prohibiting the solution from entering the tube. 
     
     
       14. The process of claim 9 wherein the anionic surface active agent is selected from the group consisting of carboxylic acid salts, sulfuric acid esters, alkane sulfonates alkylarylsulfonates and mixtures thereof. 
     
     
       15. The process of claim 9 wherein the cationic surface active agent is selected from the group consisting of quaternary nitrogen salts, non quaternary nitrogen bases and mixtures thereof. 
     
     
       16. The process of claim 9 wherein the nonionic surface active agent is selected from the group consisting of ethylene oxide derivatives, polyhydroxy esters of sugar alcohols, amphoteric surfactants and mixtures thereof. 
     
     
       17. The process of claim 1 wherein the emulsifier is a surface active agent selected from the group consisting of isooctyl phenoxyl polyethoxy ethanol, alkoxypolyethylene oxyethanol, sodium linear alkyl sulfonate, laury ethoxylate sulfate, stearyl-dimethylbenzylammonium chloride and mixtures thereof. 
     
     
       18. The process of claim 9 wherein the emulsifier solution has about the same hydrophilic-lipophilic balance as the grafted electrochemical cell separator to be emulsified. 
     
     
       19. The process of claim 1 wherein said emulsifier is employed as an aqueous solution. 
     
     
       20. The process of claim 19 wherein said emulsifier comprises about 1-2% of said aqueous solution by weight. 
     
     
       21. The process of claim 19 wherein the residence time of said separator in the aqueous emulsifier solution is from a few seconds to about five minutes. 
     
     
       22. The process of claim 20 wherein the residence time of said separator in the aqueous emulsifier solution is about two minutes. 
     
     
       23. The process of claim 19 wherein the temperature of said aqeuous emulsifier solution is from about 80° C. to 90° C. 
     
     
       24. The process of claim 19 wherein said aqueous emulsifier solution comprises a mixture of an anionic and a non-ionic emulsifier. 
     
     
       25. The process of claim 24 wherein said mixture of an anionic and non-ionic emulsifier consists of from about 25% to 50% anionic emulsifier and from about 50% to 75% non-ionic emulsifier. .Iadd. 
     
     
       26.  The process of claim 1 wherein said organic solvent is selected from the group consisting of toluene and chlorinated organic hydrocarbons. .Iaddend. .Iadd.27. The process of claim 26 wherein said emulsifier is a surface active agent selected from the group of anionics, cationics and non-ionics. .Iaddend. .Iadd.28. The process of claim 27 wherein the anionic surface active agent is selected from the group consisting of carboxylic acid salts, sulfuric acid esters, alkane sulfonates, alkylaryl sulfonates and mixtures thereof. .Iaddend. .Iadd.29. The process of claim 27 wherein the cationic surface active agent is selected from the group consisting of quaternary nitrogen salts, non-quaternary nitrogen bases and mixtures thereof. .Iaddend. .Iadd.30. The process of claim 27 wherein the nonionic surface active agent is selected from the group consisting of ethylene oxide derivatives, polyhydroxy esters of sugar alcohols, amphoteric surfactants and mixtures thereof. .Iaddend.