US 11,702,491 B2
Membrane including fluoropolymer hybrid organic/inorganic composite, and electrochemical device having the same
Gaëlle Besnard, Grenoble (FR); Elise Gutel, Veurey-Voroize (FR); Hélène Rouault, Le Versoud (FR); Julio A. Abusleme, Saronno (IT); Ségolène Brusseau, Tavaux (FR); Marc-David Braida, Bry-sur-Marne (FR); Djamel Mourzagh, Sassenage (FR); and Daniel Tomasi, Villard Saint Christophe (FR)
Assigned to Solvay SA, Brussels (BE); and Commissariat à l'Énergie Atomique et aux Énergies Aternatives, Paris (FR)
Appl. No. 16/771,660
Filed by SOLVAY SA, Brussels (BE); and COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES, Paris (FR)
PCT Filed Dec. 11, 2018, PCT No. PCT/EP2018/084296
§ 371(c)(1), (2) Date Jun. 10, 2020,
PCT Pub. No. WO2019/115500, PCT Pub. Date Jun. 20, 2019.
Claims priority of application No. 17306762 (EP), filed on Dec. 13, 2017.
Prior Publication US 2021/0087314 A1, Mar. 25, 2021
Int. Cl. C08F 214/22 (2006.01); H01M 50/403 (2021.01); H01M 50/426 (2021.01); H01M 50/446 (2021.01); C08K 5/5415 (2006.01); C08K 5/5435 (2006.01); H01M 10/0525 (2010.01)
CPC C08F 214/225 (2013.01) [C08K 5/5415 (2013.01); C08K 5/5435 (2013.01); H01M 10/0525 (2013.01); H01M 50/403 (2021.01); H01M 50/426 (2021.01); H01M 50/446 (2021.01)] 20 Claims
 
1. A membrane for an electrochemical device, said membrane comprising:
(a) at least one polymer (F-h), wherein the at least one polymer (F-h) is at least one fluoropolymer hybrid organic/inorganic composite comprising inorganic domains, said hybrid being obtained by reaction between:
at least one polymer (F), wherein the at least one polymer (F) is at least one fluoropolymer comprising:
(i) recurring units derived from at least one fluorinated monomer (FM),
(ii) recurring units derived from at least one (meth)acrylic monomer (MA) of formula:

OG Complex Work Unit Chemistry
wherein each of R1, R2, R3, equal or different from each other, is independently a hydrogen atom or a C1-C3 hydrocarbon group, and ROHis a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group, and
(iii) optionally recurring units derived from at least one fluorinated monomer (FM2) different from VDF;
wherein the at least one polymer (F) has an intrinsic viscosity measured in dimethylformamide at 25° C. higher than 0.90 dl/g and lower than 6.0 dl/g; and
at least one metal compound (M) of formula (I):
X4-mAYm  (I)
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, X is a hydrocarbon group, optionally comprising one or more functional groups,
wherein the inorganic domains are obtained by grafting at least one metal compound (M) to the polymer (F) through reaction of said at least one metal compound (M) with at least a fraction of the ROH groups of the (meth)acrylic monomer (MA); and
(b) a liquid medium (L).