IP Library Granted Patent US 12,199,287
Granted Patent B2
US 12,199,287 · App. 17/263,721 · Granted Jan 14, 2025

Anode for Li-ion battery

Inventors: Dominique Plee (Colombes, FR); Fabrice Domingues Dos Santos (Colombes, FR); Gregory Schmidt (Pierre-Benite, FR)
Assignee: ARKEMA FRANCE
H01M4/628C08F214/222C08L27/16H01M4/0402H01M4/134H01M4/1395H01M4/366H01M4/382H01M10/0525C08L2203/206C08L2205/025
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Quick Facts
Patent No.
US 12,199,287
App. No.
17/263,721
Granted
Jan 14, 2025
Kind
B2
Abstract

The invention relates to an anode for a Li-ion rechargeable battery, said anode being covered with a protective film based on fluorinated copolymer(s). The invention also relates to the processes for preparing this anode. The invention also relates to a Li-ion rechargeable battery comprising an anode according to the invention. The invention lastly relates to the use of fluorinated copolymer(s) as film for covering an anode for a lithium-ion battery comprising a negative electrode active material.

Claims (27)

1. Anode for lithium-ion battery, comprising a negative electrode active material, said anode being covered with a film comprising at least one copolymer chosen from:

the copolymer comprising vinylidene fluoride and trifluoroethylene units of formula P(VDF-TrFE),

the copolymer comprising vinylidene fluoride and tetrafluoroethylene units of formula P(VDF-TFE), and

a fluorinated terpolymer chosen from: the terpolymer comprising vinylidene fluoride, trifluoroethylene and chlorofluoroethylene units of formula P(VDF-TrFE-CFE), the terpolymer comprising vinylidene fluoride, trifluoroethylene and chlorotrifluoroethylene units of formula P(VDF-TrFE-CTFE), the terpolymer comprising vinylidene fluoride, trifluoroethylene and hexafluoropropylene units of formula P(VDf-TrFE-HFP), the terpolymer comprising vinylidene fluoride, tetrafluoroethylene and chlorofluoroethylene units of formula P(VDF-TFE-CFE), the terpolymer comprising vinylidene fluoride, tetrafluoroethylene and chlorotrifluoroethylene units of formula P(VDF-TFE-CTFE), and the terpolymer comprising vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene units of formula P(VDf-TFE-HFP),

or a blend chosen from: the blend of P(VDF-TrFE) copolymer with the P(VDF-TFE) copolymer; the blend of P(VDF-TrFE) copolymer with one of the aforementioned terpolymers; the blend of P(VDF-TFE) copolymer with one of the aforementioned terpolymers, and the blend of two terpolymers among the aforementioned ones;

in which the negative electrode active material is an alkali metal.

2. Anode according to claim 1 , in which the negative electrode active material is lithium.

3. Anode according to claim 1 , in which said film has a thickness ranging from 1 to 14 μm, limits included.

4. Anode according to claim 1 , in which said film has a density ranging from 1.2 to 2 g/cm 3 .

5. Anode according to claim 1 , in which, when the fluorinated film deposited on said negative electrode active material is formed of a blend of a copolymer and a terpolymer, these are present in a weight ratio of from 50:50 to 1:99.

6. Anode according to claim 1 , in which, in the copolymer of formula P(VDF-TrFE), the proportion of units derived from trifluoroethylene is less than 55 mol % and greater than 18 mol % relative to the sum of the units derived from vinylidene fluoride and from trifluoroethylene.

7. Anode according to claim 1 , in which, in the copolymer of formula P(VDF-TFE), the proportion of units derived from tetrafluoroethylene is less than 60 mol % and greater than 10 mol % relative to the sum of the units derived from vinylidene fluoride and from tetrafluoroethylene.

8. Anode according to claim 1 , in which the molar ratio of the VDF units to the TrFE or TFE units in the terpolymers has a value of from 85/15 to 30/70.

9. Anode according to claim 1 , in which the proportion of units derived from the CFE, HFP or CTFE monomer is from 1 to 15 mol %, relative to all of the units of a terpolymer.

10. Process for manufacturing a negative electrode comprising a layer of negative electrode active material covered with a film of fluorinated copolymer(s) according to claim 1 , said process comprising a step of depositing said film of fluorinated copolymer(s) on the surface of said negative electrode active material.

11. Process according to claim 10 , in which the deposition of the film takes place via a solvent route.

12. Process according to claim 10 comprising a step consisting in dissolving the fluorinated copolymer or the fluorinated terpolymers in a solvent selected from the group consisting of carbonates, carbamates, nitriles, amides, sulfoxides, sulfolane, nitromethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1,H)-pyrimidinone, 3-methyl-2-oxazolidinone, and mixtures thereof.

13. Process according to claim 10 , in which the deposition of the film takes place via a dry route.

14. Li-ion rechargeable battery comprising the negative electrode according to claim 1 , a positive electrode and an electrolyte.

15. A film for covering an anode for a lithium-ion battery comprising a negative electrode active material, the film comprising a copolymer chosen from:

the copolymer comprising vinylidene fluoride and trifluoroethylene units of formula P(VDF-TrFE),

the copolymer comprising vinylidene fluoride and tetrafluoroethylene units of formula P(VDF-TFE), and

a fluorinated terpolymer chosen from: the terpolymer comprising vinylidene fluoride, trifluoroethylene and chlorofluoroethylene units of formula P(VDF-TrFE-CFE), the terpolymer comprising vinylidene fluoride, trifluoroethylene and chlorotrifluoroethylene units of formula P(VDF-TrFE-CTFE), the terpolymer comprising vinylidene fluoride, trifluoroethylene and hexafluoropropylene units of formula P(VDf-TrFE-HFP), the terpolymer comprising vinylidene fluoride, tetrafluoroethylene and chlorofluoroethylene units of formula P(VDF-TFE-CFE), the terpolymer comprising vinylidene fluoride, tetrafluoroethylene and chlorotrifluoroethylene units of formula P(VDF-TFE-CTFE), and the terpolymer comprising vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene units of formula P(VDf-TFE-HFP),

or of a blend chosen from: the blend of P(VDF-TrFE) copolymer with the P(VDF-TFE) copolymer; the blend of P(VDF-TrFE) copolymer with one of the aforementioned terpolymers; the blend of P(VDF-TFE) copolymer with one of the aforementioned terpolymers, and the blend of two terpolymers among the aforementioned ones;

wherein the film is configured to inhibit the formation of lithium dendrites within the negative electrode active material.

16. Anode according to claim 1 , wherein the at least one copolymer has a melt flow index between 0.1 and 100.

17. The film according to claim 15 , wherein the copolymer has a melt flow index between 0.1 and 100.

Assignments (2)
CHANGE OF ADDRESS Recorded Jul 4, 2025
From: ARKEMA FRANCE
To: ARKEMA FRANCE
Reel/Frame 071814/0739 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 5, 2022
From: PLEE, DOMINIQUE; DOMINGUES DOS SANTOS, FABRICE; SCHMIDT, GREGORY
To: ARKEMA FRANCE
Reel/Frame 058549/0638 →