Hybrid fluoropolymer composites

Patent metadata

Field	Value
Publication number	US-10414890-B2
Application number	US-201816028152-A
Country	US
Kind code	B2
Filing date	Jul 5, 2018
Priority date	May 7, 2014
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

The present invention pertains to a fluoropolymer hybrid organic/inorganic composite, to a process for manufacturing said fluoropolymer hybrid organic/inorganic composite and films and membranes thereof and to uses of said fluoropolymer hybrid organic/inorganic composite and films and membranes thereof in various applications.

First claim

The invention claimed is:

1. A polymer electrolyte membrane comprising at least one fluoropolymer hybrid organic/inorganic composite [polymer (F-h)] and an electrolyte medium comprising at least one metal salt [medium (E)], wherein polymer (F-h) includes fluoropolymer domains and inorganic domains and comprises at least one grafted fluoropolymer [polymer (F-g)] comprising recurring units derived from at least one fluorinated monomer [monomer (F)] and at least one hydrogenated monomer [monomer (HH)], said monomer (HH) comprising:
at least one pendant side chain comprising an end group of formula —O—C(O)—NH—Z-AY m X 3-m (M1-g), wherein m is an integer from 1 to 3, Y is a hydrolysable group, A is a metal selected from the group consisting of Si, Ti and Zr, X is a hydrocarbon group comprising at least one —N═C═O functional group and Z is a hydrocarbon group, optionally comprising at least one —N═C═O functional group, and
optionally, at least one pendant side chain comprising an end group of formula —O-A′Y′ m′-1 X′ 4-m′ (M2-g), wherein m′ is an integer from 1 to 4, Y′ is a hydrolysable group, A′ is a metal selected from the group consisting of Si, Ti and Zr, X′ is a hydrocarbon group, optionally comprising at least one functional group different from the —N═C═O functional group,
and wherein the inorganic domains are obtained by hydrolysing and/or condensing the end groups of formula —O—C(O)—NH—Z-AY m X 3-m (M1-g) and, optionally, the end groups of formula —O-A′Y′ m′-1 X′ 4-m′ (M2-g) of polymer (F-g).

2. An electrochemical device comprising the polymer electrolyte membrane according to claim 1 .

3. The polymer electrolyte membrane according to claim 1 , wherein the medium (E) comprises at least one metal salt and at least one organic carbonate.

4. The polymer electrolyte membrane according to claim 1 , wherein the medium (E) comprises at least one metal salt, at least one ionic liquid and, optionally, at least one organic carbonate.

5. The polymer electrolyte membrane according to claim 1 , wherein the metal salt is selected from the group consisting of MeI, Me(PF 6 ) n , Me(BF 4 ) n , Me(ClO 4 ) n , Me(bis(oxalato)borate) n (“Me(BOB) n ”), MeCF 3 SO 3 , Me[N(CF 3 SO 2 ) 2 ] n , Me[N(C 2 F 5 SO 2 ) 2 ] n , Me[N(CF 3 SO 2 )(R F SO 2 )] n with R F being C 2 F 5 , C 4 F 9 , CF 3 OCF 2 CF 2 , Me(AsF 6 ) n , Me[C(CF 3 SO 2 ) 3 ] n , Me 2 S n , wherein Me is a metal and n is the valence of said metal.

6. The polymer electrolyte membrane according to claim 5 , wherein Me is a transition metal, an alkaline metal or an alkaline-earth metal.

7. The polymer electrolyte membrane according to claim 6 , wherein Me is selected from Li, Na, K, and Cs.

8. The polymer electrolyte membrane according to claim 1 , wherein polymer (F-g) further comprises recurring units derived from at least one hydrogenated monomer [monomer (H)].

9. The polymer electrolyte membrane according to claim 1 , wherein the at least one monomer (F) comprises vinylidene fluoride (VDF) optionally in combination with at least one monomer different from VDF.

10. The polymer electrolyte membrane according to claim 1 , wherein the at least one monomer (F) comprises a combination of tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), and at least one monomer (H) selected from ethylene, propylene and isobutylene, optionally in combination with one or more additional monomers.

Assignees

• Solvay
• Commissariat Energie Atomique

Inventors

• Ducros Jean-Baptiste
• Lavie-Cambot Aurelie
• Picard Lionel
• Pras Olivier
• Rouault Helene
• Hamon Christine
• Abusleme Julio A

Classifications

• C08F220/20

  of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} · CPC title

• C08G18/6229 Primary

  Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• C08G18/718

  containing silicon · CPC title

• H01M10/0565

  Polymeric materials, e.g. gel-type or solid-type · CPC title