Lithium metal negative electrode and lithium metal battery including the same

Patent metadata

Field	Value
Publication number	US-12046746-B2
Application number	US-202017271659-A
Country	US
Kind code	B2
Filing date	Jul 15, 2020
Priority date	Jul 16, 2019
Publication date	Jul 23, 2024
Grant date	Jul 23, 2024

Abstract

A lithium metal negative electrode and a lithium metal battery including the lithium metal negative electrode. The lithium metal negative electrode includes a protective layer present on at least one surface of the negative electrode for stabilizing between the lithium metal and the electrolyte. The protective layer includes a polymer of alpha lipoic acid (ALA) and sulfur molecule (S8), a depolymerized product of the polymer, an inorganic sulfide-based compound, and at least one of an inorganic nitride-based compound, or an inorganic nitrate-based compound.

First claim

The invention claimed is:

1. A lithium metal negative electrode comprising:
a negative electrode; and
a protective layer present on the negative electrode,
wherein the protective layer comprises:
a polymer of alpha lipoic acid (ALA) and an octagonal-ring shaped sulfur molecule (S 8 ),
a depolymerized product of the polymer,
an inorganic sulfide-based compound, and
at least one of an inorganic nitride-based compound or an inorganic nitrate-based compound.

2. The lithium metal negative electrode according to claim 1 , wherein
the inorganic sulfide-based compound comprises at least one of Li 2 S or Li 2 S 2 .

3. The lithium metal negative electrode according to claim 1 , wherein
the inorganic nitride-based compound comprises Li 3 N, and
the inorganic nitrate-based compound comprises LiN x O y
wherein x=1 or 2, and y=2 or 3.

4. The lithium metal negative electrode according to claim 1 , wherein
the polymer is obtained by polymerizing alpha lipoic acid and octagonal-ring shaped sulfur molecules in a weight ratio of 10:1 to 1:10.

5. The lithium metal negative electrode according to claim 1 , wherein
the polymer of alpha lipoic acid (ALA) and octagonal-ring shaped sulfur molecule (S 8 ) is represented by the following Chemical Formula 1:

in the Chemical Formula 1, R 1 to R 4 are each independently a substituted or unsubstituted C1 to C3 alkylene group;
3≤n≤10; and 1<x≤10.

6. The lithium metal negative electrode according to claim 1 , wherein
the depolymerized product of the polymer is an oligomer represented by at least one of the following Chemical Formula 1-1 or a monomer represented by the following Chemical Formula 1-2:

in the Chemical Formula 1-1, R 1 to R 4 are each independently a substituted or unsubstituted C1 to C3 alkylene group;
1≤y≤6; and
1≤z≤5,

in the Chemical Formula 1-2, R 1 to R 4 are each independently a substituted or unsubstituted C1 to C3 alkylene group.

7. The lithium metal negative electrode according to claim 6 , wherein
the oligomer and the monomer each independently further comprise a lithium cation.

8. The lithium metal negative electrode according to claim 1 , wherein
the negative electrode is a lithium free anode consisting of only a copper current collector; or
the negative electrode comprises:
a copper current collector and a lithium metal layer present on the copper current collector.

9. A lithium metal battery comprising:
the lithium metal negative electrode of claim 1 ;
a positive electrode;
a separator located between the lithium metal negative electrode and the positive electrode; and
an electrolyte impregnated in the separator, wherein the electrolyte comprises a lithium salt, an organic solvent, and LiNO 3 .

10. The lithium metal battery according to claim 9 , further comprising
a coating layer comprising the polymer is present on at least one surface facing the negative electrode among both surfaces of the separator facing the negative electrode.

11. The lithium metal battery according to claim 9 , wherein a concentration of the LiNO 3 in the electrolyte is 0.1 M to 1.0 M.

12. The lithium metal battery according to claim 9 , wherein
the lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

13. The lithium metal battery according to claim 9 , wherein
the organic solvent is a mixture of 1,3-dioxolane (DOL) and dimethoxyethane (DME) in a volume ratio of 3:7 to 7:3.

14. A method for producing a lithium metal battery comprising the steps of:
preparing a polymer of alpha lipoic acid (ALA) and an octagonal-ring shaped sulfur molecule (S 8 );
coating the polymer onto one surface of a separator;
preparing an electrode assembly wherein the separator surface coated with the polymer is positioned opposite to a lithium metal negative electrode, and another surface of the separator is positioned opposite to a positive electrode,
injecting an electrolyte into the separator in the electrode assembly; and
packaging the electrode assembly after injecting the electrolyte to obtain the lithium metal battery.

15. The method for producing a lithium metal battery according to claim 14 , wherein
in the obtained lithium metal battery,
a part of the polymer coated on the surface of the separator is depolymerized by reacting the polymer with the lithium metal of the negative electrode,
another part of the polymer coated on the surface of the separator is reduced and decomposed by reacting with the electrolyte, and
wherein the electrolyte comprises LiNO 3 and the LiNO 3 is reduced and decomposed by reacting with the lithium metal of the negative electrode.

16. The method for producing a lithium metal battery according to claim 14 , wherein
heat is applied at a temperature in a range of 150° C. to 175° C. to a mixture of the alpha lipoic acid (ALA) and the octagonal-ring shaped sulfur molecule (S 8 ) in the step of preparing a polymer.

Assignees

• Lg Chemical Ltd
• Korea Advanced Inst Sci & Tech
• Lg Energy Solution Ltd

Inventors

• Yoon Jong Keon
• Kim Yunjung
• YUN Hyunwoong
• Hwang Sunwoo
• Hah Hoejin
• Kim Hee-Tak
• Roh Youngil

Classifications

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M10/0525

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

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M4/5815

  Sulfides · CPC title