	US 12,469,872 B2
	Fluoropolymer hybrid composite
Alberto Frache, Alessandria (IT); Silvia Santangeletta, Alluvioni Piovera (IT); Daniele Battegazzore, Alessandria (IT); Julio A. Abusleme, Saronno (IT); Christine Hamon, Bollate (IT); Giambattista Besana, Mariano Comense (IT); and Sëgolène Brusseau, Tavaux (FR)
Assigned to SYENSQO SA, Brussels (BE); and Politecnico di Torino, Turin (IT)
Appl. No. 17/297,028
Filed by SYENSQO SA, Brussels (BE); and POLITECNICO DI TORINO, Turin (IT)
PCT Filed Dec. 16, 2019, PCT No. PCT/EP2019/085246 § 371(c)(1), (2) Date May 26, 2021, PCT Pub. No. WO2020/126975, PCT Pub. Date Jun. 25, 2020.
Claims priority of application No. 18306704 (EP), filed on Dec. 17, 2018.
Prior Publication US 2021/0408574 A1, Dec. 30, 2021
Int. Cl. H01M 10/056 (2010.01)

CPC H01M 10/056 (2013.01) [H01M 2300/0091 (2013.01)]

16 Claims

1. A process for manufacturing a polymer electrolyte based on a fluoropolymer hybrid organic/inorganic composite, said process comprising the following steps:

(i) providing a composition comprising a pre-gelled metal compound [compound (P-GM)] obtained by partially hydrolysing and/or polycondensing a metal compound [compound (M)] having formula:

X4-mAYm

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 selected from the group consisting of an alkoxy group, an acyloxy group and a hydroxyl group, X is a hydrocarbon group, optionally comprising one or more functional groups; in the presence of:

an electrolyte solution [solution (ES)] comprising at least one metal salt [metal salt(S)] and a liquid medium [medium (L)];

at least one acid catalyst; and

optionally, an aqueous medium;

said pre-gelled metal compound [compound (P-GM)] comprising one or more inorganic domains consisting of ≡A-O-A≡ bonds and one or more residual hydrolysable groups Y; and then

(ii) reacting in the molten state at least a fraction of hydroxyl groups of a functional fluoropolymer comprising at least one hydroxyl group [polymer (F)] with at least a fraction of hydrolysable groups Y of said compound (P-GM), so as to obtain a polymer electrolyte comprising a fluoropolymer hybrid organic/inorganic composite incorporating the electrolyte solution (ES)

wherein the polymer electrolyte has a uniform atomic element distribution having an incorporation of silicon of not more than 61% difference from the theoretical expected value, as measured by energy dispersive spectroscopy analysis by scanning electron microscopy according to

SiO₂[%]=[[SiO2]/([SiO2]+[F])]×100 (1)

wherein [SiO2] and [F] from equation (1) are calculated using the following equations (2) and (3), respectively:

[SiO2]=([Si_EDS]×60)/28 (2)

[F]=([FEDS]×64)/38 (3)

wherein:

Si_EDSand F_EDSare the weight % of Si and F obtained by EDS, 60 is the molecular weight of SiO2, 28 is the atomic weight of Si, 64 is the molecular weight of CH₂═CF₂, and 38 is the atomic weight of two F elements.