Fluoropolymer film

Patent metadata

Field	Value
Publication number	US-10227462-B2
Application number	US-201314395852-A
Country	US
Kind code	B2
Filing date	Apr 22, 2013
Priority date	Apr 23, 2012
Publication date	Mar 12, 2019
Grant date	Mar 12, 2019

Abstract

The invention pertains to a process for manufacturing a fluoropolynner film comprising a fluoropolymer hybrid organic/inorganic composite, said process comprising the following steps: (i) providing a mixture of: —at least one fluoropolymer [polymer (F)]; —at least one metal compound [compound (M)] having formula: X 4-m AY m wherein m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, Y is a hydrolysable group and X is a hydrocarbon group, optionally comprising one or more functional groups; —a liquid medium consisting essentially of at least one ionic liquid (IL) and, optionally, at least one additive (A); —optionally, at least one electrolytic salt (ES); and —optionally, at least one organic solvent (S); (ii) hydrolyzing and/or polycondensing said compound (M) to yield a liquid mixture comprising fluoropolymer hybrid organic/inorganic composite comprising inorganic domains and incorporating said liquid medium; (iii) processing a film from the liquid mixture obtained in step (ii); and (iv) drying and then, optionally, curing the film obtained in step (iii) for obtaining the fluoropolymer film. The invention also pertains to the fluoropolymer film obtained from said process and to use of said fluoropolymer film in electrochemical and photo-electrochemical devices.

First claim

The invention claimed is:

1. A fluoropolymer film comprising a fluoropolymer hybrid organic/inorganic composite, wherein said hybrid is obtained by a process comprising hydrolysing and/or polycondensing a mixture comprising:
at least one fluoropolymer [polymer (F)];
at least one compound [compound (M)] having formula:
X 4-m AY m

wherein m is an integer from 1 to 4, A is an element selected from the group consisting of Si, Ti and Zr, Y is a hydrolysable group and X is a hydrocarbon group, optionally comprising one or more functional groups; and
a liquid medium consisting of at least one ionic liquid (IL) and, optionally, at least one additive (A) selected from organic carbonates and mixtures thereof.

2. The fluoropolymer film according to claim 1 , wherein polymer (F) is a polymer (F-2) comprising recurring units derived from vinylidene fluoride (VDF) and, optionally, from one or more fluorine-containing monomers different from VDF.

3. The fluoropolymer film according to claim 1 , wherein polymer (F) comprises recurring units derived from at least one (meth)acrylic monomer [monomer (MA)] having formula (I):

wherein each of R 1 , R 2 , R 3 , equal to or different from each other, is independently a hydrogen atom or a C 1 -C 3 hydrocarbon group and R OH is a C 1 -C 5 hydrocarbon moiety comprising at least one hydroxyl group.

4. The fluoropolymer film according to claim 1 , said film further comprising at least one electrolytic salt (ES) different from said ionic liquid (IL).

5. A metal-ion secondary battery comprising as polymer electrolyte separator the fluoropolymer film according to claim 1 , said fluoropolymer film comprising at least one electrolytic salt (ES) different from said ionic liquid (IL).

6. A metal-ion capacitor comprising as polymer electrolyte separator the fluoropolymer film according to claim 1 , said fluoropolymer film comprising at least one electrolytic salt (ES) different from said ionic liquid (IL).

7. A dye-sensitized solar cell comprising as polymer electrolyte separator the fluoropolymer film according to claim 1 , said fluoropolymer film comprising at least one electrolytic salt (ES) different from said ionic liquid (IL).

8. A photochromic device comprising as polymer electrolyte separator the fluoropolymer film according to claim 1 , said fluoropolymer film comprising at least one electrolytic salt (ES) different from said ionic liquid (IL).

9. An electrochromic device comprising as polymer electrolyte separator the fluoropolymer film according to claim 1 , said fluoropolymer film comprising at least one electrolytic salt (ES) different from said ionic liquid (IL).

10. A fuel cell comprising as polymer separator the fluoropolymer film according to claim 1 , said fluoropolymer film comprising a liquid medium consisting essentially of at least one protic ionic liquid (IL p ) and, optionally, at least one additive (A) selected from organic carbonates and mixtures thereof.

11. A process for manufacturing the fluoropolymer film according to claim 1 , said process comprising:
(i) providing a mixture comprising:
the at least one fluoropolymer [polymer (F)];
the at least one compound [compound (M)] having formula:
X 4-m AY m

wherein m is an integer from 1 to 4, A is an element selected from the group consisting of Si, Ti and Zr, Y is a hydrolysable group and X is a hydrocarbon group, optionally comprising one or more functional groups; and
the liquid medium consisting of at least one ionic liquid (IL) and, optionally, at least one additive (A) selected from the group consisting of organic carbonates and mixtures thereof;

(ii) hydrolysing and/or polycondensing said compound (M) to yield a liquid mixture comprising a fluoropolymer hybrid organic/inorganic composite comprising inorganic domains and incorporating said liquid medium;
(iii) processing a film from the liquid mixture obtained in step (ii); and
(iv) drying and then, optionally, curing the film obtained in step (iii) to obtain the fluoropolymer film.

12. The process according to claim 11 , wherein polymer (F) comprises recurring units derived from at least one (meth)acrylic monomer [monomer (MA)] having formula (I):

wherein each of R 1 , R 2 , R 3 , equal to or different from each other, is independently a hydrogen atom or a C 1 -C 3 hydrocarbon group and R OH is a C 1 -C 5 hydrocarbon moiety comprising at least one hydroxyl group.

13. The process according to claim 11 , wherein the amount of one or more ionic liquids (IL) in the liquid medium is such that the mixture of step (i) comprises at least 1% by weight and at most 95% by weight of ionic liquids (IL) based on the total weight of the polymer (F) and the ionic liquid (IL) in said mixture.

14. The process according to claim 11 , wherein the ionic liquid (IL) in the liquid medium is selected from protic ionic liquids (IL p ), aprotic ionic liquids (IL a ) and mixtures thereof.

15. The process according to claim 11 , wherein under step (i) the mixture further comprises:
at least one organic solvent (S) different from said ionic liquid (IL) and said additive (A).

16. The process according to claim 11 , wherein under step (iii) the film is manufactured by casting the liquid mixture onto a support surface, said support surface being made of a composition comprising:
at least one polymer (F) having a melting temperature of at least 180° C.; and
from 0.1% to 30% by weight of mica.

17. The process according to claim 13 , wherein the mixture of step (i) comprises at least 5% by weight and at most 85% by weight of ionic liquids (IL) based on the total weight of the polymer (F) and the ionic liquid (IL) in said mixture.

18. The process according to claim 13 , wherein the mixture of step (i) comprises at least 10% by weight and at most 75% by weight of ionic liquids (IL) based on the total weight of the polymer (F) and the ionic liquid (IL) in said mixture.

19. The process according to claim 16 , wherein under step (iii) the film is manufactured by casting the liquid mixture onto a support surface, said support surface being made of a composition comprising:
at least one polymer (F) having a melting temperature of at least 200° C.; and
from 1% to 10% by weight of mica.

Assignees

• Solvay
• Centre Nat Rech Scient

Inventors

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

Classifications

• H01M10/0569

  characterised by the solvents · CPC title

• H01M8/1037

  having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes · CPC title

• H01M8/1044

  Mixtures of polymers, of which at least one is ionically conductive · CPC title

• H01M8/1051

  Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2 · CPC title

• H01M2300/0045

  Room temperature molten salts comprising at least one organic ion · CPC title