Fluoropolymer film

Patent metadata

Field	Value
Publication number	US-11530306-B2
Application number	US-201716312272-A
Country	US
Kind code	B2
Filing date	Jun 1, 2017
Priority date	Jun 20, 2016
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

The invention pertains to a process for the manufacture of a fluoropolymer film, to the fluoropolymer film obtainable therefrom and to use of said fluoropolymer film in electrochemical and photo-electrochemical devices.

First claim

The invention claimed is:

1. A process for manufacturing a fluoropolymer film comprising a fluoropolymer composite, said process comprising:
processing a mixture to obtain a film, wherein the mixture is a mixture of:
at least one fluoropolymer having an intrinsic viscosity higher than 1.5 dl/g, wherein the intrinsic viscosity is measured in DMF at 25° C.;
at least one liquid medium (LM) containing at least one ionic liquid (IL) and containing at least one electrolytic salt (ES) and, optionally at least one organic solvent (S);

and
heating the film obtained at a temperature between 120° C. and 200° C. to obtain a transparent film;
wherein the film obtained has an elongation at break of at least of 200% and a stress at break of at least 15 MPa.

2. The process according to claim 1 , wherein polymer (F) has intrinsic viscosity higher than 2.0 dl/g, wherein the intrinsic viscosity is measured in DMF at 25° C.

3. The process according to claim 2 , wherein polymer (F) has intrinsic viscosity higher than 2.5 dl/g, wherein the intrinsic viscosity is measured in DMF at 25° C.

4. The process according to claim 1 , wherein heating the film is carried out for not less than 5 minutes.

5. The process according to claim 1 , wherein the ionic liquid (IL) is selected from those comprising a cation selected from a sulfonium ion or an imidazolium, pyridinium, pyrrolidinium or piperidinium ring, said ring being optionally substituted on the nitrogen atom and on the carbon atoms, and comprising an anion selected from halides anions, perfluorinated anions and borates.

6. The process according to claim 5 , wherein said ring is substituted on the nitrogen atom by one or more alkyl groups with 1 to 8 carbon atoms, on the carbon atoms by one or more alkyl groups with 1 to 30 carbon atoms, or on both.

7. The process according to claim 1 , wherein the electrolytic salt (ES) is selected from LiI, LiPF 6 , LiBF 4 , LiClO 4 , lithium bis(oxalato)borate (“LiBOB”), LiCF 3 SO 3 , LiN(CF 2 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , M [N(CF 3 SO 2 )(R F SO 2 )] n with R F being C 2 F 5 , C 4 F 9 , or CF 3 OCF 2 CF 2 , LiAsF 6 , LiC(CF 3 SO 2 ) 3 , Li 2 S n , and combinations thereof.

8. The process according to claim 1 , wherein the liquid medium (LM) comprises an organic solvent (S) selected from the group consisting of ketones; polar aprotic solvents comprising oxygen and/or nitrogen heteroatom(s); organic phosphates and mixtures thereof.

9. The process according to claim 8 , wherein the liquid medium (LM) comprises an organic solvent (S) selected from the group consisting of acetone, methylethylketone, isophorone, methyl isobutyl ketone (MIK), cyclohexanone, diisobutyl ketone, N,N-dimethylformamide (DMF), N,N dimethyl acetamide, tetramethyl urea, dimethylsulfoxide (DMSO), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), trimethyl phosphate, triethyl phosphate and mixtures thereof.

10. The process according to claim 1 , wherein:
the ionic liquid (IL) is selected from those comprising a cation selected from a sulfonium ion or an imidazolium, pyridinium, pyrrolidinium or piperidinium ring, said ring being optionally substituted on the nitrogen atom and on the carbon atoms, and comprising an anion selected from halides anions, perfluorinated anions and borates;
the electrolytic salt (ES) is selected from LiI, LiPF 6 , LiBF 4 , LiClO 4 , lithium bis(oxalato)borate (“LiBOB”), LiCF 3 SO 3 , LiN(CF 2 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , M [N(CF 3 SO 2 )(R F SO 2 )] n with R F being C 2 F 5 , C 4 F 9 , or CF 3 OCF 2 CF 2 , LiAsF 6 , LiC(CF 3 SO 2 ) 3 , Li 2 S n , and combinations thereof; and
the liquid medium (LM) comprises an organic solvent (S) selected from the group consisting of ketones; amides; polar aprotic solvents comprising oxygen and/or nitro gen heteroatom (s); organic phosphates and mixtures thereof.

11. The process according to claim 10 , wherein:
in the ionic liquid (IL), said ring is substituted on the nitrogen atom by one or more alkyl groups with 1 to 8 carbon atoms, on the carbon atoms by one or more alkyl groups with 1 to 30 carbon atoms, or on both; and
the liquid medium (LM) comprises an organic solvent (S) selected from the group consisting of acetone, methylethylketone, isophorone, methyl isobutyl ketone (MIK), cyclohexanone diisobutyl ketone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetramethyl urea, dimethylsulfoxide (DMSO), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), trimethyl phosphate, triethyl phosphate and mixtures thereof.

12. A fluoropolymer film which is obtainable by the process of claim 1 .

Assignees

• Solvay
• Centre Nat Rech Scient

Inventors

• Hamon Christine
• Abusleme Julio A
• Guyomard-Lack Aurélie
• Le Bideau Jean
• Guyomard Dominique
• Lestriez Bernard

Classifications

• C08F214/225

  with non-fluorinated comonomers · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• H01G11/52 Primary

  Separators · CPC title