	US 12,136,744 B2
	Hybrid fluoropolymer electrolyte membrane
Dominique Bascour, Grez-Doiceau (BE); Guillaume Müller, Woluwe-Saint-Pierre (BE); and Menouar Mazouzi, Brussels (BE)
Assigned to SYENSQO SA, Brussels (BE)
Appl. No. 17/637,471
Filed by SYENSQO SA, Brussels (BE)
PCT Filed Jul. 28, 2020, PCT No. PCT/EP2020/071265 § 371(c)(1), (2) Date Feb. 23, 2022, PCT Pub. No. WO2021/052663, PCT Pub. Date Mar. 25, 2021.
Claims priority of application No. 19197491 (EP), filed on Sep. 16, 2019.
Prior Publication US 2022/0278422 A1, Sep. 1, 2022
Int. Cl. H01M 50/00 (2021.01); H01M 10/052 (2010.01); H01M 50/403 (2021.01); H01M 50/446 (2021.01)

CPC H01M 50/446 (2021.01) [H01M 10/052 (2013.01); H01M 50/403 (2021.01)]

14 Claims

1. A process for manufacturing a fluoropolymer electrolyte membrane comprising a fluoropolymer hybrid organic/inorganic composite for an electrochemical device, said process comprising the steps of:

a) dissolving i) at least one fluoropolymer in ii) at least one liquid medium, wherein the i) at least one fluoropolymer comprises

at least one first recurring unit derived from at least one ethylenically unsaturated fluorinated monomer and

at least one second recurring unit derived from at least one ethylenically unsaturated monomer having at least one hydroxyl group;

b) reacting at least a fraction of the hydroxyl groups of the i) at least one fluoropolymer with iii) at least one metal compound of formula (I)

X_4-mAY_m (I)

wherein m is an integer from 1 to 3, 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 comprising at least one isocyanate (—N═C═O) functional group, thereby providing a composition comprising at least one grafted fluoropolymer comprising at least one hydrogenated monomer having at least one pendant side chain comprising an end group of formula —O—C(O)—NH—Z—AY_mX_3-m, wherein m, Y, A and X have the same meaning as defined above and Z is a hydrocarbon group, optionally comprising at least one —N═C═O functional group;

c) reacting the end group of formula —O—C(O)—NH—Z—AY_mX_3-mwith iv) at least one metal compound of formula (II)

X′_4-m′A′Y′_m′ (II)

wherein m′ is in integer from 1 to 4, A′ is a metal selected from the group consisting of Si, Ti and Zr, Y′ is a hydrolysable group, optionally comprising at least one functional group different from the —N═C═O group, and X′ is a hydrocarbon group, thereby providing a composition comprising at least one fluoropolymer hybrid organic/inorganic composite; and

d) processing the composition from step c) into a polymer electrolyte membrane, characterized by the absence of a drying step.