IP Library › Granted Patent US 11,133,523
Granted Patent B2
US 11,133,523 · App. 15/663,262 · Granted Sep 28, 2021

Aqueous electrolytes with protonic ionic liquid and batteries using the electrolyte

Inventors: Kensuke Takechi (Ann Arbor, MI); Ruidong Yang (Ann Arbor, MI)
Assignee: TOYOTA MOTOR ENGINEERING & MANUFACTURING NORTH AMERICA, INC.
H01M10/0525H01M10/0563H01M10/0566H01M10/36H01M2220/20H01M2300/0002H01M2300/0008H01M2300/0011H01M2300/0014
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Quick Facts
Patent No.
US 11,133,523
App. No.
15/663,262
Granted
Sep 28, 2021
Kind
B2
Abstract

An aqueous electrolyte composition suitable for a lithium ion battery is provided. The aqueous electrolyte composition contains water, an ionic liquid which is a salt of a protonic cation and an anion comprising a fluoroalkylsulfonyl group and a lithium fluoroalkylsulfonyl salt. A lithium ion battery containing the aqueous electrolyte and a vehicle at least partially powered by the battery are also provided.

Claims (38)

1. An aqueous electrolyte for a lithium-ion secondary battery comprising:

water;

a lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I):

R—SO 2 —  (1)

wherein R is a perfluoroalkyl group of 1-5 carbons; and

an ionic liquid which is a salt of a protonic cation and an anion comprising a fluoroalkylsulfonyl group of formula (I) and wherein the protonic cation is selected from the group consisting of the following formulae:

wherein R 1 is —H, and

R 2 , R 3 and R 4 are each independently an alkyl group having 1-6 carbons, being linear, branched or cyclic; wherein

the aqueous electrolyte is in contact with an anode active material capable of intercalation and de-intercalation of lithium ions.

2. The aqueous electrolyte for a lithium secondary battery of claim 1 , wherein the lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I) is at least one salt selected from the group consisting of lithium bis(trifluoromethyl-sulfonyl)imide (LiTFSI), lithium bis(pentafluoroethyl-sulfonyl)imide (LiBETI), lithium bis(fluoromethylsulfonyl)imide (LiFSI) and lithium trifluoromethylsulfonate (LiTFS).

3. The aqueous electrolyte for a lithium secondary battery of claim 1 , wherein the protonic cation is at least one is selected from the group consisting of the following formulae:

and

the anion comprising a fluoroalkylsulfonyl group of formula (I) is at least one anion selected from the group consisting of bis(trifluoromethyl-sulfonyl)imide (TFSI), bis(pentafluoroethyl-sulfonyl)imide (BETI), bis(fluoromethylsulfonyl)imide (FSI) and trifluoromethylsulfonate (TFS); wherein R 1 is —H, and

R 2 , R 3 and R 4 are each independently an alkyl group having 1-6 carbons, being linear, branched or cyclic.

4. The aqueous electrolyte for a lithium secondary battery of claim 1 , wherein a mole ratio relationship of lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I), water and ionic liquid is such that for 1 mole of the lithium salt, there are 0.1 to 20 mole of ionic liquid and 0.1 to 10 mole water.

5. The aqueous electrolyte for a lithium secondary battery of claim 1 , wherein a concentration of the lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I) is from 2 M to 20 M.

6. A lithium ion battery comprising:

an anode having an active material capable of intercalation and de-intercalation of lithium ions wherein the active material is compatible with an aqueous electrolyte and has a redox potential greater than 0.5 V vs Li/Li + ;

a cathode capable of intercalation and de-intercalation lithium ions; and

an aqueous electrolyte in contact with the anode active material and cathode which comprises:

water;

a lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I):

R—SO2-  (1)

wherein R is a perfluoroalkyl group of 1-5 carbons; and

an ionic liquid which is a salt of a protonic cation and an anion comprising a fluoroalkylsulfonyl group of formula (I) and wherein the protonic cation comprises at least one structure selected from the group consisting of the following formulae:

wherein R 1 is —H, and

R 2 , R 3 and R 4 are each independently an alkyl group having 1-6 carbons, being linear, branched or cyclic.

7. The lithium ion battery of claim 6 , wherein the lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I) is at least one salt selected from the group consisting of lithium bis(trifluoromethyl-sulfonyl)imide (LiTFSI), lithium bis(pentafluoroethyl-sulfonyl)imide (LiBETI), lithium bis(fluoromethylsulfonyl)imide (LiFSI) and lithium trifluoromethylsulfonate (LiTFS).

8. The lithium ion battery of claim 6 , wherein the protonic cation of the ionic liquid is at least one is selected from the group consisting of the following formulae:

and

the anion comprising a fluoroalkylsulfonyl group of formula I) of the ionic liquid is at least one anion selected from the group consisting of bis(trifluoromethyl-sulfonyl)imide (TFSI), bis(pentafluoroethyl-sulfonyl)imide (BETI), bis(fluoromethylsulfonyl)imide (FSI) and trifluoromethylsulfonate (TFS); wherein R 1 is —H, and

R 2 , R 3 and R 4 are each independently an alkyl group having 1-6 carbons, being linear, branched or cyclic.

9. The lithium ion battery of claim 6 , wherein a mole ratio relationship of the lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I), water and ionic liquid is such that for 1 mole of the lithium salt, there are 0.1 to 20 mole of ionic liquid and 0.1 to 10 mole water.

10. The lithium ion battery of claim 6 , wherein a concentration of the lithium salt of an anion comprising a fluoroalkylsulfonyl group of formula (I) is from 2 M to 20 M.

11. The lithium ion battery of claim 6 , wherein the cathode capable of intercalation and de-intercalation lithium ions comprises at least one compound selected from the group consisting of LiMn 2 O 4 , LiCoO 2 , LiFe 2 (PO 4 ), LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiNi 0.5 Mn 1.5 O 4 and LiCoPO 4 .

12. The lithium ion battery of claim 6 , wherein the anode capable of intercalation and de-intercalation of lithium ions comprises at least one active material selected from the group consisting of Li 4 Ti 5 O 12 , elemental Sulfur, Mo 6 S 8 , Cu 2 V 2 O 7 , TiS 4 , NbS 5 and Li terephthalate.

13. A vehicle, comprising the battery of claim 6 .

14. The aqueous electrolyte for a lithium secondary battery of claim 1 , wherein the anode capable of intercalation and de-intercalation of lithium ions comprises at least one active material selected from the group consisting of Li 4 Ti 5 O 12 , elemental Sulfur, Mo 6 S 8 , Cu 2 V 2 O 7 , TiS 4 , NbS 5 and Li terephthalate.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 26, 2021
From: TOYOTA MOTOR ENGINEERING & MANUFACTURING NORTH AMERICA, INC.
To: KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO
Reel/Frame 058252/0164 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 28, 2017
From: TAKECHI, KENSUKE; YANG, RUIDONG
To: TOYOTA MOTOR ENGINEERING & MANUFACTURING NORTH AMERICA, INC.
Reel/Frame 043133/0809 →
Continuity (1)
Related Publication 20190036151A1 · Jan 31, 2019
Cited By (1)
US 12,322,758