Electrode-forming composition

Patent metadata

Field	Value
Publication number	US-10333146-B2
Application number	US-201214344486-A
Country	US
Kind code	B2
Filing date	Sep 6, 2012
Priority date	Sep 13, 2011
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

The invention pertains to an aqueous electrode-forming composition comprising:—at least one fluoropolymer [polymer (F)];—particles of at least one powdery active electrode material [particles (P)], said particles (P) comprising a core of an active electrode compound [compound (E)] and an outer layer of a metallic compound [compound (M)] different from Lithium, said outer layer at least partially surrounding said core; and—water, to a process for its manufacture, to a process for manufacturing an electrode structure using the same, to an electrode structure made from the same and to an electrochemical device comprising said electrode structure.

First claim

The invention claimed is:

1. An aqueous electrode-forming composition comprising:
at least one polymer (F), wherein polymer (F) is a fluoropolymer;
particles of at least one powdery active electrode material (P), said particles (P) comprising a core of an active electrode compound (E) and an outer layer of a metallic compound (M) different from Lithium, said outer layer surrounding said core,
wherein compound (M) is one of Rh, Ir, Ru, Ti, Re, Os, Cd, Tl, Pb, Bi, In, Sb, Al, Ti, Cu, Ni, Pd, V, Fe, Cr, Mn, Co, Zn, Mo, W, Ag, Au, Pt, Ir, Ru, Pd, Sn, Ge, and Ga or is an alloy of one or more of Rh, Ir, Ru, Ti, Re, Os, Cd, Tl, Pb, Bi, In, Sb, Al, Ti, Cu, Ni, Pd, V, Fe, Cr, Mn, Co, Zn, Mo, W, Ag, Au, Pt, Ir, Ru, Pd, Sn, Ge, and Ga,
wherein compound (E) is different from compound (M) and is an active cathode compound (E+) selected from the group consisting of composite metal chalcogenides represented by a general formula of LiMY 2 , wherein M denotes at least one transition metal, selected from Co, Ni, Fe, Mn, Cr and V; and Y denotes a chalcogen, selected from O and S; and

water.

2. The aqueous electrode-forming composition of claim 1 , wherein polymer (F) is a vinylidene fluoride (VDF) polymer comprising:
(a′) at least 50% by moles of recurring units derived from vinylidene fluoride (VDF);
(b′) optionally from 0.1 to 20% by moles of a fluorinated monomer different from VDF; and
(c′) optionally from 0.1 to 10%, by moles, based on the total amount of monomers (a′) and (b′), of one or more hydrogenated monomer(s).

3. The aqueous electrode-forming composition of claim 2 , wherein polymer (F) is a VDF polymer comprising recurring units derived from vinylidene fluoride (VDF) and from at least one (meth)acrylic monomer (MA) having formula (I):

wherein:
R 1 , R 2 and R 3 , equal to or different from each other, are independently selected from a hydrogen atom and a C 1 -C 3 hydrocarbon group, and
ROH is a hydrogen atom or a C 1 -C 5 hydrocarbon moiety comprising at least one hydroxyl group.

4. The aqueous electrode-forming composition of claim 1 , wherein compound (E+) is selected from the group consisting of LiCoO 2 , LiNiO 2 , LiMnO 2 , LiNi x Co 1−x O 2 (wherein 0<x<1), and Li x Co 1−y Al y O 2 (wherein 0<x<1 and 0<y<1).

5. The aqueous electrode-forming composition of claim 1 , wherein the compound (M) comprises at least one of Rh, Ir, Ru, Ti, Re, Os, Cd, Tl, Pb, Bi, In, Sb, Al, Ti, Cu, Ni, Pd, V, Fe, Cr, Mn, Co, Zn, Mo, W, Ag, Au, Pt, Ir, Ru, Pd, Sn, Ge, or Ga.

6. The aqueous electrode-forming composition of claim 5 , wherein the compound (M) is Cu, Ag or an alloy of Ag and/or of Cu.

7. The aqueous electrode-forming composition of claim 1 , said composition additionally comprising at least one electroconductivity-imparting additive.

8. The aqueous electrode-forming composition of claim 1 , said composition being substantially free from additional liquid solvent different from water.

9. A process for manufacturing the electrode-forming composition of claim 1 , said process comprising mixing polymer (F) and particles (P), and optionally other ingredients, in an aqueous medium.

10. The process of claim 9 , wherein mixing of polymer (F), particles (P) and all optional ingredients is performed by an apparatus selected from a roll kneader, a mixer, a homo mixer, a ball mixer, a bead mill.

11. A process for manufacturing an electrode structure, said process comprising applying the electrode-forming composition of claim 1 onto at least one surface of a substrate.

12. The process of claim 11 , wherein the electrode-forming composition is applied by a wet coating process selected from screen printing, coating using a roll coater, a blade coater, a slit coater, a curtain coater, a wire coater, a sprayer, a foam applicator, and a brush coater.

13. An electrode structure made from the electrode-composition of claim 1 .

14. An electrochemical device comprising an electrode structure according to claim 13 .

15. The aqueous electrode-forming composition of claim 2 , wherein polymer (F) is a vinylidene fluoride (VDF) polymer comprising:
(a′) at least 80% by moles of recurring units derived from vinylidene fluoride (VDF);
(b′) optionally from 0.1 to 10% by moles of a fluorinated monomer different from VDF; and
(c′) optionally from 0.1 to 3% by moles, based on the total amount of monomers (a′) and (b′), of one or more hydrogenated monomer(s).

16. The aqueous electrode-forming composition of claim 15 , wherein the fluorinated monomer different from VDF is selected from vinylfluoride (VF 1 ), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), tetrafluoroethylene (TFE), perfluoromethylvinylether (MVE), trifluoroethylene (TrFE) and mixtures thereof.

17. The aqueous electrode-forming composition of claim 7 , wherein the electroconductivity-imparting additive is at least one additive selected from carbon black, graphene or carbon nanotubes, and powders and fibers of metals, including nickel and aluminium.

18. An aqueous electrode-forming composition comprising:
at least one polymer (F), wherein polymer (F) vinylidene fluoride (VDF) polymer comprising:
(a′) at least 80% by moles of recurring units derived from vinylidene fluoride (VDF), and
(c′) from 0.1 to 3% by moles of at least one (meth)acrylic monomer (MA) having formula (I):

wherein:
R 1 , R 2 and R 3 , equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and
R OH is a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group;
particles of at least one powdery active electrode material (P), said particles (P) comprising a core of an active cathode compound (E+) selected from the group consisting of composite metal chalcogenides represented by general formula LiMY 2 , wherein M denotes one or more transition metals selected from Co, Ni, Fe, Mn, Cr and V, and Y denotes O or S, and
an outer layer of a metallic compound (M) selected from Cu, Ag, an alloy of Ag, an alloy of Cu and mixtures thereof, said outer layer at least partially surrounding said core; and
water.

Assignees

• Cojocaru Paula
• Pieri Riccardo
• Apostolo Marco
• Solvay Specialty Polymers It

Inventors

• Cojocaru Paula
• Pieri Riccardo
• Apostolo Marco

Classifications

• H01M4/621

  Binders · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/623 Primary

  fluorinated polymers · CPC title

• H01M4/0414

  by screen printing · CPC title