Lithium metal battery electrolytes and electrochemical cells including the same

Patent metadata

Field	Value
Publication number	US-11784349-B2
Application number	US-202117220058-A
Country	US
Kind code	B2
Filing date	Apr 1, 2021
Priority date	Apr 1, 2021
Publication date	Oct 10, 2023
Grant date	Oct 10, 2023

Abstract

An electrolyte for a lithium metal battery including a nonaqueous aprotic organic solvent and a lithium salt dissolved or ionized in the nonaqueous aprotic organic solvent. The nonaqueous aprotic organic solvent includes a cyclic carbonate, an acyclic carbonate, and an acyclic fluorinated ether. The lithium salt includes an aliphatic fluorinated disulfonimide lithium salt.

First claim

What is claimed is:

1. An electrolyte for a lithium metal battery, the electrolyte comprising:
a nonaqueous aprotic organic solvent; and
a lithium salt dissolved or ionized in the nonaqueous aprotic organic solvent,
wherein the nonaqueous aprotic organic solvent includes a cyclic carbonate, an acyclic carbonate, and an acyclic fluorinated ether having the formula:

wherein n=0 or 1,
wherein R 1 and R 2 are each straight-chain C1-C6 fluoroalkyl groups,
wherein, when n=1, R 3 is a methylene group or a polyethylene group, and
wherein the lithium salt comprises lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide.

2. The electrolyte of claim 1 wherein the total number of carbon atoms in the acyclic fluorinated ether is 2, 3, 4, 5, 6, or 7.

3. The electrolyte of claim 1 wherein n=0, wherein R 1 is a perfluoromethyl group or a perfluoroethyl group, and wherein R 2 is a perfluoromethyl group or a perfluoroethyl group.

4. The electrolyte of claim 1 wherein n=1, R 1 and R 2 are each perfluoroethyl groups, and R 3 is an ethylene group.

5. The electrolyte of claim 1 wherein the acyclic fluorinated ether is at least one of bis(2,2,2-trifluoroethyl) ether, 2,2,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)propane, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, 1-(2,2-difluoroethoxy)-1,1,2,2-tetrafluoroethane, 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, or 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane, and wherein the acyclic fluorinated ether accounts for, by volume, from 5% to 50% of the nonaqueous aprotic organic solvent.

6. The electrolyte of claim 1 wherein the cyclic carbonate is at least one of ethylene carbonate, fluoroethylene carbonate, difluoro ethylene carbonate, or 3,3,3-trifluoropropylene carbonate, and wherein the acyclic carbonate is at least one of diethyl carbonate, dimethyl carbonate, or ethyl methyl carbonate.

7. The electrolyte of claim 1 wherein the lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide is present in the nonaqueous aprotic organic solvent at a concentration in a range of from 0.1 M to 1.0 M.

8. The electrolyte of claim 1 further comprising a second lithium salt dissolved or ionized in the nonaqueous aprotic organic solvent, wherein the second lithium salt comprises at least one of LiClO 4 , LiBF 4 , or LiPF 6 , and wherein, in combination, the lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide and the second lithium salt are present in the nonaqueous aprotic organic solvent at a concentration in a range of from 0.5 M to 2.0 M.

9. The electrolyte of claim 5 wherein the cyclic carbonate accounts for, by volume, from 10% to 40% of the nonaqueous aprotic organic solvent, the acyclic carbonate accounts for, by volume, from 60% to 80% of the nonaqueous aprotic organic solvent, and wherein the acyclic fluorinated ether, the cyclic carbonate, and the acyclic carbonate account for, by volume, 100% of the nonaqueous aprotic organic solvent.

10. The electrolyte of claim 1 further comprising an anti-corrosion additive of lithium difluoro(oxalate)borate, lithium bis(oxalato)borate, lithium perchlorate, or lithium 2-trifluoromethyl-4,5-dicyanoimidazole, wherein the anti-corrosion additive accounts for, by weight, from 0.1% to 5% of the electrolyte.

11. An electrochemical cell comprising:
a negative electrode made of nonporous lithium metal;
a positive electrode spaced apart from the negative electrode, the positive electrode including at least one transition metal oxide that can undergo a reversible intercalation of lithium ions; and
an electrolyte in ionic contact with the negative and positive electrodes, the electrolyte including:
a nonaqueous aprotic organic solvent;
a first lithium salt dissolved or ionized in the nonaqueous aprotic organic solvent, the first lithium salt including an aliphatic fluorinated disulfonimide lithium salt; and
a second lithium salt dissolved or ionized in the nonaqueous aprotic organic solvent;
wherein the nonaqueous aprotic organic solvent includes a cyclic carbonate, an acyclic carbonate, and an acyclic fluorinated ether, and
wherein the aliphatic fluorinated disulfonimide lithium salt comprises lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide.

12. The electrochemical cell of claim 11 wherein the negative electrode comprises, by weight, greater than 97% lithium.

13. The electrochemical cell of claim 11 wherein the second lithium salt comprises at least one of LiClO 4 , LiBF 4 , or LiPF 6 , and wherein a ratio of the first lithium salt to the second lithium salt in the electrolyte is less than one.

14. The electrochemical cell of claim 11 wherein the acyclic fluorinated ether has the formula:

wherein n=0 or 1,
wherein R 1 and R 2 are each straight-chain C1-C6 fluoroalkyl groups,
wherein, when n=1, R 3 is a methylene group or a polyethylene group, and
wherein the total number of carbon atoms in the acyclic fluorinated ether is 2, 3, 4, 5, 6, or 7.

15. The electrochemical cell of claim 11 wherein the cyclic carbonate is at least one of ethylene carbonate, fluoroethylene carbonate, difluoro ethylene carbonate, or 3,3,3-trifluoropropylene carbonate, and wherein the acyclic carbonate is at least one of diethyl carbonate, dimethyl carbonate, or ethyl methyl carbonate.

16. The electrochemical cell of claim 15 wherein the acyclic fluorinated ether is at least one of bis(2,2,2-trifluoroethyl) ether, 2,2,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)propane, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, 1-(2,2-difluoroethoxy)-1,1,2,2-tetrafluoroethane, 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, or 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane, and wherein the acyclic fluorinated ether accounts for, by volume, from 5% to 50% of the nonaqueous aprotic organic solvent.

17. The electrochemical cell of claim 16 wherein the cyclic carbonate accounts for, by volume, from 10% to 40% of the nonaqueous aprotic organic solvent, the acyclic carbonate accounts for, by volume, from 60% to 80% of the nonaqueous aprotic organic solvent, and wherein the acyclic fluorinated ether, the cyclic carbonate, and the acyclic carbonate account for, by volume, 100% of the nonaqueous aprotic organic solvent.

18. The electrochemical cell of claim 11 wherein the electrolyte in ionic contact with the negative and positive electrodes consists of the nonaqueous aprotic organic solvent, the first lithium salt, the second lithium salt, and optionally an anti-corrosion additive, and wherein the nonaqueous aprotic organic solvent consists of the cyclic carbonate, the acyclic carbonate, and the acyclic fluorinated ether.

Assignees

• Gm Global Tech Operations Llc

Inventors

• He Meinan
• Cai Mei
• Chen Shuru

Classifications

• H01M10/0568 Primary

  characterised by the solutes · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title