# US 2014/0154573 A1 · Aqueous vinylidene fluoride polymer latex

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- Number: US 2014/0154573 A1
- Document ID: US20140154573A1
- Status: Published application
- Kind: A1
- Application number: 14/232,894
- Filed: 2012-07-13
- Published: 2014-06-05
- Earliest claimed: 2011-07-15
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Inventors: Milena Stanga; Riccardo Pieri; Anna Maria Bertasa; Bradley Lane Kent; Giulio Brinati
- Web page: https://patentgrep.com/patent/US20140154573A1

## CPC

- H01M 4/623: {fluorinated polymers}
- C08L 27/16: Homopolymers or copolymers or vinylidene fluoride
- C09D 127/16: Homopolymers or copolymers of vinylidene fluoride
- H01M 4/0402: {Methods of deposition of the material}
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/1393: of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/622: {being polymers}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention pertains to an aqueous composition comprising: (A) an aqueous latex comprising at least one vinylidene fluoride (VDF) polymer [polymer (F)] comprising recurring units derived from vinylidene fluoride (VDF) and at least one (meth)acrylic monomer (MA) having formula (I) here below: wherein: —R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and —ROH is a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group, (B) at least one powdery electrode material, and (C) optionally, less than 10% by weight, based on the total weight of the aqueous composition, of at least one organic solvent (S), wherein the polymer (F) in the N aqueous latex is under the form of primary particles having an average primary particle size of less than 1 μm, as measured according to ISO 13321. The present invention also pertains to a process for manufacturing an electrode using said aqueous composition, to an electrode comprising a metal substrate coated on at least one surface with said aqueous composition and to use of said electrode for manufacturing a non-aqueous-type electrochemical device.

## Claims

### Claim 1

An aqueous composition comprising:
(A) an aqueous latex comprising at least one vinylidene fluoride (VDF) polymer (F) comprising recurring units derived from vinylidene fluoride (VDF) and at least one (meth)acrylic monomer (MA) of formula (I):
wherein:
R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and
ROH is a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group,
(B) at least one powdery electrode material, and
(C) optionally, less than 10% by weight, based on the total weight of the aqueous composition, of at least one organic solvent (S),
wherein the polymer (F) in the aqueous latex is in the form of primary particles having an average primary particle size of less than 1 μm, as measured according to ISO 13321.

### Claim 2 (depends on 1)

The aqueous composition according to claim 1, wherein the aqueous latex is prepared by aqueous emulsion polymerization in an aqueous medium of vinylidene fluoride (VDF) and at least one (meth)acrylic monomer (MA) having formula (I), optionally in the presence of at least one other comonomer (C).

### Claim 3 (depends on 1)

The aqueous composition according to claim 1, wherein the aqueous latex has homogeneously dispersed therein primary particles of at least one polymer (F) having an average primary particle size of less than 1 μm, as measured according to ISO 13321.

### Claim 4 (depends on 1)

The aqueous composition according to claim 1, wherein the (meth)acrylic monomer (MA) complies with formula (II):
wherein:
R′1, R′2 and R′3 are hydrogen atoms, and
R′OH is a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group.

### Claim 5 (depends on 1)

The aqueous composition according to claim 1, wherein the (meth)acrylic monomer (MA) is acrylic acid (AA).

### Claim 6 (depends on 1)

The aqueous composition according to claim 1, consisting of:
(A) an aqueous latex consisting of:
from 10% to 50% by weight, based on the total weight of the aqueous latex, of at least one polymer (F), and
optionally, at least one surfactant selected from a fluorinated surfactant (FS), a hydrogenated surfactant (H) and mixtures thereof, and
(B) from 20% to 80% by weight, based on the total weight of the aqueous composition, of at least one powdery electrode material,
wherein the polymer (F) in the aqueous latex is under in the form of primary particles having an average primary particle size comprised between 50 nm and 600 nm, as measured according to ISO 13321.

### Claim 7 (depends on 1)

The aqueous composition according to claim 1, wherein the aqueous latex is prepared by an aqueous emulsion polymerization process without any subsequent coagulation step.

### Claim 8

A process for manufacturing an electrode, said process comprising:
(i) providing an aqueous latex comprising at least one vinylidene fluoride (VDF) polymer (F), said polymer (F) comprising recurring units derived from vinylidene fluoride (VDF) and at least one (meth)acrylic monomer (MA) of formula (I):
wherein:
R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and
ROH is a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group;
(ii) admixing said aqueous latex with at least one powdery electrode material, optionally in the presence of one or more additives, to provide an aqueous electrode-forming composition;
(iii) applying said aqueous electrode-forming composition onto at least one surface of a metal substrate to provide at least one electroactive layer adhered to at least one surface of said metal substrate; and
(iv) drying said electroactive layer to provide said electrode.

### Claim 9 (depends on 8)

The process according to claim 8, wherein the aqueous electrode-forming composition is for manufacturing negative electrodes or anodes, and said composition comprises:
(a′) from 0.5% to 10% by weight, based on the total weight of (a′)+(b′)+(c′), of at least one polymer (F),
(b′) from 20% to 80% by weight, based on the total weight of (a′)+(b′)+(c′), of at least one powdery electrode material, and
(c′) optionally, up to 2% by weight, based on the total weight of (a′)+(b′)+(c′), of a thickener.

### Claim 10 (depends on 1)

An electrode comprising a metal substrate coated on at least one surface with the aqueous composition according to claim 1.

### Claim 11 (depends on 10)

The electrode according to claim 10, comprising:
from 1% to 15% by weight, based on the total weight of the electrode, of at least one polymer (F),
from 80% to 99% by weight, based on the total weight of the electrode, of at least one powdery electrode material, and
optionally, up to 10% by weight, based on the total weight of the electrode, of one or more additives.

### Claim 12 (depends on 10)

A non-aqueous-type electrochemical device comprising the electrode according to claim 10.

### Claim 13 (depends on 10)

A lithium ion secondary battery comprising the electrode according to claim 10.

### Claim 14 (depends on 10)

The electrode according to claim 10, comprising:
from 2% to 12% by weight, based on the total weight of the electrode, of at least one polymer (F),
from 85% to 98% by weight, based on the total weight of the electrode, of at least one powdery electrode material, and
optionally, up to 5% by weight, based on the total weight of the electrode, of one or more additives.

### Claim 15 (depends on 14)

The electrode according to claim 14, wherein polymer (F) comprises recurring units derived from vinylidene fluoride (VDF) and at least one (meth)acrylic monomer (MA) of formula (II):
wherein:
R′1, R′2 and R′3 are hydrogen atoms, and
R′OH is a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group.

### Claim 16 (depends on 1)

The aqueous composition according to claim 1, consisting of:
(A) an aqueous latex consisting of:
from 20% to 35% by weight, based on the total weight of the aqueous latex, of at least one polymer (F), and
optionally, at least one surfactant selected from a fluorinated surfactant (FS), a hydrogenated surfactant (H) and mixtures thereof, and
(B) from 40% to 70% by weight, based on the total weight of the aqueous composition, of at least one powdery electrode material,
wherein the polymer (F) in the aqueous latex is in the form of primary particles having an average primary particle size comprised between 80 nm and 400 nm, as measured according to ISO 13321.

### Claim 17 (depends on 16)

The aqueous composition according to claim 16, wherein the (meth)acrylic monomer (MA) complies with formula (II):
wherein:
R′1, R′2 and R′3 are hydrogen atoms, and
R′OH is a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group.

### Claim 18 (depends on 16)

The aqueous composition according to claim 16, wherein the (meth)acrylic monomer (MA) is acrylic acid (AA).