Microporous films

• US 5,198,162 A
• Filed: 06/13/1989
• Issued: 03/30/1993
• Est. Priority Date: 12/19/1984
• Status: Expired due to Fees

• Current Assignee: SciMat Limited (Crane Company)
• Original Assignee: SciMat Limited (Crane Company)
• Inventors: Cook, John A., Park, George B., Barker, David J., McLoughlin, Robert H., Dorling, Mike G. L.
• Primary Examiner(s): Dawson, Robert A.
• Assistant Examiner(s): Kuhns, Allan R.
• Application Number:
  US07/367,740
• Time in Patent Office: 1,386 Days
• Field of Search: 264/41, 264/49, 264/DIG. 60, 264/46.1, 264/46.3
• US Class Current: 264/49
• CPC Class Codes: C08J 2201/0444 Salts
• CPC Class Codes: C08J 2201/0464 using water or inorganic fluids
• CPC Class Codes: C08J 2323/04 Homopolymers or copolymers of ethene
• CPC Class Codes: C08J 2327/12 containing fluorine atoms
• CPC Class Codes: C08J 9/26 by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
• CPC Class Codes: C25B 13/08 based on organic materials
• CPC Class Codes: H01M 2300/0017 Non-aqueous electrolytes
• CPC Class Codes: H01M 2300/002 Inorganic electrolyte
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 50/426 Fluorocarbon polymers
• CPC Class Codes: H01M 50/491 Porosity
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A microporous polymeric film of high porosity comprises a halopolymer in which the repeating units are --(C_n H_2n)-- and --(C_m X_2m)-- in which each X independently represents fluorine or chlorine and the values of n and m are greater than one and less than six. The film is the result of firstly melt processing a mixture of the halopolymer, more than 150 parts by weight of an extractable salt and not more than 80 parts by weight of an extractable polymer per 100 parts by weight of the halopolymer, the extractable polymer not being completely and homogeneously mixed with the halopolymer and being less viscous than the halopolymer when both are molten so that the surfaces of the film resulting from melt processing are rich in the extractible polymer, and secondly extracting at least some of the extractable salt to render the film porous and extracting at least some of said polymer to impart surface porosity to the film. The film has a porosity of more than 50% by volume and more usually 60-70%. The film may be used as the separator of an electrochemical cell e.g. a battery having a lithium anode and a thionyl chloride electrolyte.

Claims

1. A method of making a polymeric film which comprises melt processing into a film of polymer composition comprising:

(a) a halopolymer in which the repeat units are --(C_n H_2n)-- and --(C_m X_2m)-- where each X independently represents fluorine or chlorine and the values of n and m are greater than one and less than six; and

(b) an extractable component comprising an extractable salt and an extractable polymer which are substantially insoluble in said halopolymer, said extractable polymer migrating preferably toward the surface of said film during said melt processing;

and subsequently extracting at least some of the extractable component so as to produce a film having a porosity of not less than about 20% by volume, said extraction of said extractable polymer imparting surface porosity to said film.

2. A method as claimed in claim 1, in which the extractable salt is present in an amount measured in parts by weight which is greater than the amount of said extractable polymer.

3. A method as claimed in claim 2, in which the extractable salt is present in an amount of from 10 to 150 parts per 100 parts of the halopolymer.

4. A method as claimed in claim 3, in which the extractable polymer, is present in an amount of not more than 60 parts per 100 parts of the halopolymer.

5. A method as claimed in claim 4, in which the extractable polymer is a homo- or copolymer of an alkylene oxide.

6. A method as claimed in claim 5, in which the extractable salt is a lithium salt.

7. A method as claimed in claim 6, in which at least some of the extractable polymer and at least some of the extractable salt are extracted from the polymer composition by means of a single solvent.

8. A method as claimed in claim 1, in which the film is deformed so as to reduce its thickness prior to extraction of the extractable component.

9. A method of making a polymeric film which comprises:

(a) mixing together a first component which is a halopolymer in which the repeating units are --(C_n H_2n)-- and --(C_m X_2m)-- in which each X independently represents fluorine or chlorine and the values of n and m are greater than one and less than six, more than 150 parts by weight per 100 parts by weight of the halopolymer of a second component which is an extractable salt comprising lithium carbonate, and not more than 80 parts by weight per 100 parts by weight of the halopolymer of a third component which is an extractable polymer selected from the group consisting of polyalkylene oxides and glycols, the extractable polymer being less viscous than the halopolymer and incompatible therewith when both are molten;

(b) melt processing the mixture to form a film in which the extractable polymer has at least partially migrated to the surfaces; and

(c) extracting at least some of the extractable salt to convert the film into a three-dimensional network structure including communicating pores and extracting at least some of said polymer to increase the number of pores opening through the major surfaces of the film, said film having a porosity of more than about 50% by volume.

10. A method according to claim 9, wherein at least some of the extractable polymer and at least some of the extractable salt are extracted from the polymer composition by means of a single solvent.

11. A method according to claim 9, wherein there is mixed with the first, second and third components at least a fourth component which is a process aid or plasticiser.

12. A method according to claim 11, wherein the process aid or plasticiser is triallyl cyanurate or triallyl isocyanurate.

13. A method according to claim 12, wherein the triallyl cyanurate or triallyl isocyanurate are mixed with the first, second and third components is an amount of 1 to 3 parts by weight per 100 parts by weight of the composition.

14. A method according to claim 9, wherein the second component is an alkylene oxide homopolymer or copolymer of molecular weight 50,000-5 million.

15. A method according to claim 9, wherein the second component is polyalkylene oxide e.g. a polyethylene oxide or polyethylene glycol that is solid at room temperature and is of molecular weight less than 1 million.

16. A method according to claim 9, wherein the second component is a polyethylene oxide of molecular weight about 100,000.

17. A method of making a polymeric film which comprises:

(a) mixing together a first component which is a halopolymer in which the repeating units are --(C_n H_2n)-- and --(C_m X_2m)-- in which each X independently represents fluorine or chlorine and the values of n and m are greater than one and less than six, more than 150 parts by weight per 100 parts by weight of said halopolymer of an extractable salt comprising lithium carbonate having a nominal upper limit of particle size of 15 microns, not more than 80 parts by weight per 100 parts by weight of the halopolymer of an extractable polymer selected from the group consisting of polyalkylene oxides and glycols, said extractable polymer being less viscous than said halopolymer and incompatible therewith when both are molten;

(b) melt processing said mixture to form a film in which said extractable polymer has at least partially migrated to the surface, and further deforming said film to reduce its thickness to less than about 75 microns; and

(c) extracting at least some of said extractable salt to convert said film into a three-dimensional network structure including communicating pores, and extracting at least some of said extractable polymer to increase the number of pores opening through the major surfaces of said film, said film having a mean pore size of greater than about 0.4 microns.

18. A method of making a polymeric film which comprises:

(a) mixing together a first component comprising a halopolymer in which the repeating units are --(C_n H_2n)-- and --(C_m X_2m)-- in which each X independently represents fluorine or chlorine and the values of n and m are greater than one and less than six, more than 150 parts by weight per 100 parts by weight of said halopolymer of an extractable salt comprising lithium carbonate, not more than 80 parts by weight per 100 parts by weight of said halopolymer of an extractable polymer selected from the group consisting of polyalkylene oxides and glycols, said extractable polymer being less viscous than said halopolymer and incompatible therewith when both are molten, the molecular weight of said extractable polymer being less than about one million;

(b) melt processing the mixture to form a film in which said extractable polymer has at least partially migrated to the surface and further deforming said film to reduce its thickness to less than about 75 microns; and

(c) extracting at least some of said extractable salt to convert said film into a three-dimensional network structure including communicating pores, and extracting at least some of said extractable polymer to increase the number of pore openings through the major surfaces of said film, said film having a porosity of not less than about 55% by volume and an airflow through said film of at least about 200 cm³ cm^-2 min^-1 at 20 psi.