Method for recycling the electrolyte of a Li-ion battery and method for recycling Li-ion batteries

Patent metadata

Field	Value
Publication number	US-10497993-B2
Application number	US-201515326778-A
Country	US
Kind code	B2
Filing date	Jul 21, 2015
Priority date	Jul 22, 2014
Publication date	Dec 3, 2019
Grant date	Dec 3, 2019

Abstract

The invention relates to a method for recycling the electrolyte of a lithium-ion battery and a method for recycling lithium-ion batteries. The method for recycling an electrolyte of the invention is a method for recycling an electrolyte containing a lithium salt of formula LiA, where A represents an anion selected from PF6, CF3SO3, BF4, ClO4 and [(CF3SO2)2]N of a Li-ion battery, characterized in that it comprises the following steps: a) optionally, treatment of the battery in order to recover the electrolyte that it contains; b) addition of water to the electrolyte; c) optionally, when step a) is carried out, filtration (F1) in order to separate the liquid phase containing the electrolyte from the solid phase comprising the residues of the battery; d) addition of an additional organic solvent to the liquid phase obtained in step b) or, when step a) is carried out, after the filtration (F1) of step c); e) decantation of the liquid phase obtained after step b) of adding water or step d) of adding additional organic solvent, whereby an aqueous phase containing the lithium salt and an organic phase containing the electrolyte solvents and the additional organic solvent are obtained; f) distillation of the organic phase obtained in step e) in order to separate the solvents of the electrolyte and the additional organic solvent; g) precipitation of the anion A of the lithium salt by addition of pyridine followed by filtration (F2); h) addition of at least one carbonate salt and/or of at least one phosphate salt to the filtrate obtained in step g) followed by filtration (F3 whereby a lithium salt and water are obtained. The invention finds its application in the field of recycling lithium-ion batteries, and more particularly the electrolyte of such batteries.

First claim

The invention claimed is:

1. A method for recycling an electrolyte containing a lithium salt of formula LiA, where A represents an anion selected from PF 6 − , CF 3 SO 3 − , BF 4 − , ClO 4 − and [(CF 3 SO 2 ) 2 ]N − of a Li-ion battery, comprising the following steps:
a) adding water to the electrolyte whereby obtaining a liquid phase which is a mixture of an aqueous phase and an organic phase;
b) adding an organic solvent of addition to the liquid phase obtained in step a), whereby obtaining an aqueous phase containing the lithium salt and an organic phase containing electrolyte solvents and the organic solvent of addition;
c) decanting to separate the aqueous phase from the organic phase;
d) distilling the separated organic phase obtained in step c) to separate the solvents of the electrolyte and the organic solvent of addition;
e) precipitating the anion A of the lithium salt by addition of pyridine and then filtering (F 2 );
f) adding at least one carbonate salt and/or of at least one phosphate salt to the filtrate obtained in step r) and then filtering (F 3 ), whereby a lithium salt and water are obtained.

2. The method as claimed in claim 1 , wherein step a) is carried out at the same time as a step of processing the battery to recovery the electrolyte by cutting up the battery under a high-pressure water jet.

3. The method as claimed in claim 1 , wherein the organic solvent of addition is selected from:
dichloromethane,
acetates, selected from butyl acetate, hexyl acetate, ethyl acetate, tert-butyl acetate;
ethers, selected from 2-methoxy-2-methylpropane, 2-ethoxy-2-methylpropane, 2-methoxy-2-methylbutane, and
ketones.

4. The method as claimed in claim 1 , wherein the organic solvent of addition obtained after distillation of the organic phase in step d) is recycled in step b) of a next carrying out of the method.

5. The method as claimed in claim 1 , wherein the decanting step c) is repeated.

6. The method as claimed in claim 1 , wherein the water obtained in step f) is recovered to be reused in step a) of a next carrying out of the method.

7. A method for recycling a Li-ion battery, wherein the method comprises a step of recycling the electrolyte of the Li-ion battery as claimed in claim 1 .

8. The method as claimed in claim 1 , wherein the electrolyte is composed of a binary or ternary mixture of cyclic carbonates selected from ethylene carbonate, propylene carbonate and butylene carbonate, linear or branched carbonates selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and dimethoxyethane, in which a lithium salt is dissolved, selected from lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium perchlorate and lithium tetrafluoroborate.

9. The method as claimed in claim 3 , wherein the ketone is butanone.

10. The method as claimed in claim 1 , wherein the method further comprises:
before step a), a step of processing the Li-ion battery to recover an electrolyte that it contains, and
after step a), a step of filtering (F 1 ) to separate a liquid phase containing the electrolyte from a solid phase comprising residues of the battery,
and wherein step b) is carried out on the liquid phase obtained in the step of filtering (F 1 ).

11. The method as claimed in claim 10 , wherein the step of processing the Li-ion battery is carried out by grinding the battery in a chamber under an inert atmosphere.

12. The method as claimed in claim 10 , wherein:
the step of processing the Li-ion battery is a step of grinding the battery under an inert atmosphere;
step of adding the organic solvent of addition is carried out either during or just after the step of processing the Li-ion battery;
filtering (F 1 ) is carried out after step b), and
step a) of adding water is carried out after of filtering (F 1 ).

13. A method for recycling a Li-ion battery, wherein the method comprises a step of recycling the electrolyte of the Li-ion battery as claimed in claim 10 .

14. The method as claimed in claim 13 , wherein the method further comprises a step a 1 ) in which solids from the solid phase obtained after filtering (F 1 ) are washed with water, followed by a step a 2 ) of filtering (F 4 ) for separating the liquid phase from the solid phase and a step a 3 ) of mixing the liquid phase obtained in step a 2 ) before the decanting step c) of the method for recycling the electrolyte.

Assignees

• Commissariat Energie Atomique

Inventors

• Billy Emmanuel
• Laucournet Richard

Classifications

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/54 Primary

  Reclaiming serviceable parts of waste accumulators · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M2300/004

  Three solvents · CPC title