IP Library Granted Patent US 11,114,667
Granted Patent B2
US 11,114,667 · App. 15/748,170 · Granted Sep 7, 2021

Electrode-forming composition

Inventors: Olivier Pras (Grenoble, FR); Hélène Rouault (Le Versoud, FR); Aurélie Guyomard-Lack (Saint Lambert la Potherie, FR); Jean Le Bideau (Nantes, FR); Dominique Guyomard (Sautron, FR); Bernard Lestriez (Nantes, FR); Christine Hamon (Bollate, IT); Marc-David Braida (Bry-sur-Marne, FR); Julio A. Abusleme (Saronno, IT)
Assignees: Solvay SA; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; Commissariat à l'Énergie Atomique et aux Énergies Alternatives
H01M4/623H01M4/0404H01M4/0409H01M4/62H01M10/052H01M10/056H01M10/0525H01M10/0565H01M50/403H01M50/446H01M2300/0082
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 11,114,667
App. No.
15/748,170
Granted
Sep 7, 2021
Kind
B2
Abstract

The present invention pertains to an electrode-forming composition, to use of said electrode-forming composition in a process for the manufacture of an electrode, to said electrode and to an electrochemical device comprising said electrode. The electrode-forming composition comprises at least one partially fluorinated fluoropolymer comprising recurring units derived from at least one fluorinated monomer and at least one functional hydrogenated monomer comprising at least one carboxylic acid end group, at least one electro-active compound, at least one liquid medium comprising at least one organic carbonate or at least one ionic liquid, and at least one metal salt.

Claims (55)

1. An electrochemical device being a secondary battery comprising:

a positive electrode,

a negative electrode, and

between said positive electrode and said negative electrode, a membrane, wherein:

A) at least one of said positive electrode and said negative electrode is an electrode obtainable by a process, said process comprising:

(i) providing a metal substrate;

(ii) providing an electrode-forming composition (C1) comprising:

at least one polymer (FF), wherein polymer (FF) is a partially fluorinated fluoropolymer comprising linear sequences of recurring units derived from at least one fluorinated monomer and at least one functional hydrogenated monomer comprising at least one carboxylic acid end group,

at least one electro-active compound (EA),

at least one liquid medium (L) comprising at least one organic carbonate or at least one ionic liquid, and

at least one metal salt (M);

(iii) applying the composition provided in step (ii) onto the metal substrate provided in step (i) thereby providing an assembly comprising a metal substrate coated with at least one layer consisting of said composition (C1); and

(iv) drying the assembly provided in step (iii);

wherein said electrode comprises:

the metal substrate, and

directly adhered onto said metal substrate, at least one laver (L1) consisting of a composition (C2) comprising:

at least one partially fluorinated fluoropolymer (FF) comprising linear sequences of recurring units derived from at least one fluorinated monomer and at least one functional hydrogenated monomer comprising at least one carboxylic acid end group,

at least one electroactive compound (EA),

at least one liquid medium (L) comprising at least one organic carbonate or at least one ionic liquid, and

at least one metal salt (M),

B) the membrane comprises a fluoropolymer hybrid organic/inorganic composite, said fluoropolymer hybrid organic/inorganic composite being obtained by a process comprising hydrolysing and/or condensing a composition comprising:

at least one partially fluorinated fluoropolymer,

at least one metal compound (M1) of formula (IV):

X 4-m AY m   (IV)

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,

at least one ionic liquid, and

at least one metal salt (M).

2. The electrochemical device according to claim 1 , wherein in composition (C1) the polymer (FF) is a polymer (FF-I) comprising recurring units derived from vinylidene fluoride (VDF), at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from VDF.

3. The electrochemical device according to claim 1 , wherein in composition (C1) the functional hydrogenated monomer comprising at least one carboxylic acid end group is selected from the group consisting of (meth)acrylic monomers of formula (I):

wherein each of R 1 , R 2 and R 3 , equal to or different from each other, is independently a hydrogen atom or a C 1 -C 3 hydrocarbon group.

4. The electrochemical device according to claim 1 , wherein in composition (C1) the polymer (FF) comprises at least 0.01% by moles, of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group.

5. The electrochemical device according to claim 1 , wherein the composition (C1) comprises at least 40% by weight of medium (L), based on the total weight of said medium (L) and polymer (FF).

6. The electrochemical device according to claim 1 , wherein the concentration of salt (M) in medium (L) is at least 0.01 M.

7. The electrochemical device according to claim 1 , wherein the concentration of salt (M) in medium (L) is at most 3M.

8. The electrochemical device according to claim 1 , wherein the salt (M) is selected from the group consisting of:

(a) 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 , wherein R F is C 2 F 5 , C 4 F 9 or CF 3 OCF 2 CF 2 , Me(AsF 6 ) n , Me[C(CF 3 SO 2 ) 3 ] n , Me 2 Sn, wherein Me is a metal, and n is the valence of said metal,

(b)

wherein R′ F is selected from the group consisting of F, CF 3 , CHF 2 , CH 2 F, C 2 F 4 , C 2 H 2 F 3 , C 2 H 3 F 2 , C 2 F 5 , C 3 F 7 , C 3 H 2 F 5 , C 3 H 4 F 3 , C 4 F 9 , C 4 H 2 F 7 , C 4 H 4 F 5 , C 5 F 11 , C 3 F 5 OCF 3 , C 2 F 4 OCF 3 , C 2 H 2 F 2 OCF 3 and CF 2 OCF 3 , and

(c) combinations thereof.

9. The electrochemical device according to claim 1 , wherein composition (C1) is applied onto the metal substrate by at least one method selected from casting, printing and roll coating.

10. The electrochemical device according to claim 1 , wherein the membrane comprises a fluoropolymer hybrid organic/inorganic composite, at least one liquid medium (L) and at least one metal salt (M) said fluoropolymer hybrid organic/inorganic composite being obtained by a process comprising hydrolysing and/or condensing a composition comprising:

at least one partially fluorinated fluoropolymer comprising recurring units derived from at least one functional hydrogenated monomer comprising at least one hydroxyl endgroup,

at least one metal compound (M2) of formula (V):

X′ 4-m ′A′Y′ m′   (V)

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 —N═C═O functional group,

optionally, at least one metal compound (M1) of formula (IV):

X 4-m AY m   (IV)

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,

at least one liquid medium (L), and

at least one metal salt (M).

11. The electrochemical device according to claim 4 , wherein in composition C1 the polymer (FF) comprises at least 0.05% by moles of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group.

12. The electrochemical device according to claim 11 , wherein in composition C1 the polymer (FF) comprises at least 0.1% by moles of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group.

13. The electrochemical device according to claim 6 , wherein the concentration of salt (M) in medium (L) is at least 0.025 M.

14. The electrochemical device according to claim 7 , wherein the concentration of salt (M) in medium (L) is at most 2 M.

15. The electrochemical device according to claim 14 , wherein the concentration of salt (M) in medium (L) is at least at least 0.05 M and at most 1 M.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 1, 2024
From: SOLVAY SA
To: SYENSQO SA
Reel/Frame 066406/0174 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 9, 2018
From: PRAS, OLIVIER; ROUAULT, HELENE; GUYOMARD-LACK, AURELIE; LE BIDEAU, JEAN; GUYOMARD, DOMINIQUE; LESTRIEZ, BERNARD; HAMON, CHRISTINE; ABUSLEME, JULIO A.; BRAIDA, MARC-DAVID
To: SOLVAY SA; CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; COMMISSARIAT A L' ENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
Reel/Frame 045475/0196 →