Electrolyte additive for lithium-ion battery

Patent metadata

Field	Value
Publication number	US-10193186-B2
Application number	US-201415037450-A
Country	US
Kind code	B2
Filing date	Nov 17, 2014
Priority date	Nov 20, 2013
Publication date	Jan 29, 2019
Grant date	Jan 29, 2019

Abstract

Electrolyte for a lithium-ion battery comprising at least one block copolymer, characterized in that said block copolymer comprises at least one polymeric segment A which is soluble in said electrolyte and at least one polymeric segment B having a temperature for dissolution “T” in said electrolyte, the polymeric segments A and B being present in amounts sufficient to make possible an increase in the viscosity of the electrolyte, preferably up to gelling of the electrolyte, at a temperature greater than or equal to the temperature “T”; the ionic conduction is produced by a solvent comprising the copolymer and lithium salts.

First claim

The invention claimed is:

1. An electrolyte for a lithium-ion battery comprising at least one block copolymer, wherein said block copolymer comprises at least one polymeric segment A which is soluble in said electrolyte and at least one polymeric segment B having a temperature for dissolution “T” in said electrolyte, the polymeric segments A and B being present in amounts sufficient to make possible an increase in the viscosity of the electrolyte at a temperature greater than or equal to the temperature “T”, and then the return of the electrolyte to a liquid state when the temperature of the electrolyte falls back below T,
wherein the block copolymer comprises at least one polymeric segment A chosen from the following polymers: polyacrylates, polymethacrylates, polycarbonates, polyester carbonates, polylactones, polylactams, polyesters, polyethers, soluble homopolymers and random copolymers of polyethers,
wherein the block copolymer comprises at least one polymeric segment B obtained from at least one monomer chosen from the following monomers: acrylic and methacrylic acids, N-alkylacrylamides or N-alkylmethacrylamides saccharides, vinylidene fluoride or hexafluoropropylene,
wherein the at least one polymeric segments B/ the at least one polymeric segments A molar ratio being greater than 0.5, and
wherein the electrolyte comprises at least one lithium salt and at least one organic solvent chosen from ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, tetrahydrofuran, tetraethylene glycol dimethyl ether, dimethyl ether, dioxolane, dioxane, polyethylene glycol dimethyl ether and/or nitriles or their mixture(s).

2. The electrolyte as claimed in claim 1 wherein the increase in the viscosity of the electrolyte is up to gelling of the electrolyte.

3. The electrolyte as claimed in claim 1 , wherein the temperature T is less than or equal to 80° C.

4. The electrolyte as claimed in claim 1 , in which the gelling of the electrolyte corresponds to a viscosity V at least greater than 10 Pa.s at 25° C.

5. The electrolyte as claimed in claim 1 exhibiting a conductivity C1 ranging from 10 −4 S.cm −1 to 0.1 S.cm −1 at a temperature of less than T.

6. The electrolyte as claimed in claim 1 , exhibiting a conductivity C2 of less than 10 −5 S.cm −1 at a temperature equal to or greater than T.

7. The electrolyte as claimed in claim 1 , in which the block copolymer comprising at least one polymeric segment B is a polymer chosen from poly(N-alkylacrylamides), poly(N-alkylmethacrylamides), polysaccharides, polyvinylidene fluoride and poly(vinylidene fluoride-hexafluoropropylene) copolymers.

8. The electrolyte as claimed in claim 1 , in which the block copolymer comprises at least one polymeric segment C which is insoluble in the electrolyte.

9. The electrolyte as claimed in claim 8 in which the block copolymer comprises at least one polymeric segment C chosen from saturated or unsaturated and branched or unbranched polyolefins.

10. The electrolyte as claimed in claim 8 , comprising a block copolymer in which the polymeric segments A/ polymeric segments C molar ratio ranges from 0.5 to 10.

11. The electrolyte as claimed in claim 8 , comprising a block copolymer in which the polymeric segments B/ polymeric segments C molar ratio ranges from 1 to 10.

12. The electrolyte as claimed in claim 1 , in which the block copolymer(s) is/are present in an amount ranging from 1 to 15% by weight, with respect to the total weight of the electrolyte.

13. The electrolyte as claimed in claim 8 , in which the block copolymer(s) is/are present in an amount ranging from 1 to 15% by weight, with respect to the total weight of the electrolyte.

14. A lithium-ion battery comprising the electrolyte as claimed in claim 1 .

15. A lithium-ion battery comprising the electrolyte as claimed in claim 8 .

16. Method for modulating the ionic conductivity of the electrolyte of a lithium-ion battery as a function of the temperature of said electrolyte, the method includes the step of using at least one block copolymer wherein said block copolymer comprises at least one polymeric segment A and at least one polymeric segment B such that said polymeric segment A is soluble in the electrolyte and said polymeric segment B has a temperature for dissolution “T” in said electrolyte, the polymeric segments A and B being present in amounts sufficient to make possible an increase in the viscosityof the electrolyte at a temperature greater than or equal to the temperature “T” and then the return of the electrolyte to a liquid state when the temperature of the electrolyte falls back below T,
wherein the block copolymer comprises at least one polymeric segment A chosen from the following polymers: polyacrylates, polymethacrylates, polycarbonates, polyester carbonates, polylactones, polylactams, polyesters, polyethers, soluble homopolymers and random copolymers of polyethers,
wherein the block copolymer comprises at least one polymeric segment B obtained from at least one monomer chosen from the following monomers: acrylic and methacrylic acids, N-alkylacrylamides or N-alkylmethacrylamides saccharides, vinylidene fluoride or hexafluoropropylene,
wherein the at least one polymeric segments B/ the at least one polymeric segments A molar ratio being greater than 0.5, and
wherein the electrolyte comprises at least one lithium salt and at least one organic solvent chosen from ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, tetrahydrofuran, tetraethylene glycol dimethyl ether, dimethyl ether, dioxolane, dioxane, polyethylene glycol dimethyl ether and/or nitriles or their mixture(s).

17. The method as claimed in claim 16 wherein the increase in the viscosity is up to gelling of the electrolyte.

18. The method as claimed in claim 16 , in which, at the temperature T, the conductivity of the electrolyte passes from a value C1 ranging from 10 −4 S.cm −1 to 0.1 S.cm −1 to a value C2 ranging from 10 −6 S.cm −1 to 10−5 S.cm 1 .

19. A method for modulating the viscosity of a electrolyte as a function of the temperature of said electrolyte, the method includes the step of using at least one block copolymer wherein said block copolymer comprises at least one polymeric segment A and at least one polymeric segment B such that said polymeric segment A is soluble in the electrolyte and said polymeric segment B has a temperature for dissolution “T” in said electrolyte, the polymeric segments A and B being present in amounts sufficient to make possible an increase in the viscosity, preferably up to gelling, of the electrolyte at a temperature greater than or equal to the temperature “T” and then the return of the electrolyte to a liquid state when the temperature of the electrolyte falls back below T,
wherein the block copolymer comprises at least one polymeric segment A chosen from the following polymers: polyacrylates, polymethacrylates, polycarbonates, polyester carbonates, polylactones, polylactams, polyesters, polyethers, soluble homopolymers and random copolymers of polyethers,
wherein the block copolymer comprises at least one polymeric segment B obtained from at least one monomer chosen from the following monomers: acrylic and methacrylic acids, N-alkylacrylamides or N-alkylmethacrylamides saccharides, vinylidene fluoride or hexafluoropropylene,
wherein the at least one polymeric segments B/ the at least one polymeric segments A molar ratio being greater than 0.5, and
wherein the electrolyte comprises at least

Assignees

• Commissariat Energie Atomique
• Commisariat A Lenergie Atomique Et Aux Energies Alternatives

Inventors

• Picard Lionel
• Moreau Gilles

Classifications

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M10/0564

  the electrolyte being constituted of organic materials only · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title