Lithium metal secondary battery having improved life characteristics

Patent metadata

Field	Value
Publication number	US-11777100-B2
Application number	US-202217874911-A
Country	US
Kind code	B2
Filing date	Jul 27, 2022
Priority date	Apr 6, 2018
Publication date	Oct 3, 2023
Grant date	Oct 3, 2023

Abstract

Disclosed is a lithium metal secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a protective layer interposed between the negative electrode and the separator. The protective layer comprises an additive, and wherein the additive comprises a mixture of hexagonal boron nitride (BN) flakes and an ionomer comprising a sulfur (S)-containing anionic group and fluorine (F). The sulfur (S)-containing anionic group is at least one selected from the group consisting of SO 4 2− and SO 3 − .

First claim

The invention claimed is:

1. A lithium metal secondary battery comprising:
a positive electrode;
a negative electrode;
a separator interposed between the positive electrode and the negative electrode; and
a protective layer interposed between the negative electrode and the separator,
wherein the protective layer comprises an additive, and wherein the additive comprises a mixture of hexagonal boron nitride (BN) flakes and an ionomer comprising a sulfur (S)-containing anionic group and fluorine (F), and
wherein the sulfur (S)-containing anionic group is SO 4 2− .

2. The lithium metal secondary battery according to claim 1 , wherein the protective layer is a porous polymer layer, an inorganic layer, or a laminate comprising a porous polymer layer and an inorganic layer.

3. The lithium metal secondary battery according to claim 2 , wherein the protective layer is the porous polymer layer, which comprises at least one selected from the group consisting of polyvinyl chloride, polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate, polyethylhexyl acrylate, polybutyl acrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylidene fluoride, polyvinyl acetate, polyethylene-co-vinyl acetate, polyethylene oxide, polypropylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylpullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan and carboxyl methyl cellulose.

4. The lithium metal secondary battery according to claim 2 , wherein the protective layer is the inorganic layer, which comprises at least one selected from the group consisting of SiO 2 , BaTiO 3 , Pb(Zr x Ti 1-x )O 3 (PZT, 0<x<1), Pb 1-X La x Zr 1-y Ti y O 3 (PLZT, 0<x<1, 0<y<1), (1−x)Pb(Mg 1/3 Nb 2/3 )O 3-x PbTiO 3 (PMNPT, 0<x<1), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , AlOOH, lithium lanthanum zirconium oxide (LLZO), Si 3 N 4 , TiC, TiO 2 and SiC.

5. The lithium metal secondary battery according to claim 1 , wherein the protective layer has a thickness range of from 0.1 μm to 10 μm.

6. The lithium metal secondary battery according to claim 1 , wherein the additive is used in an amount of 50 wt % to 98 wt % based on a total weight of the protective layer.

7. The lithium metal secondary battery according to claim 1 , wherein the additive comprises the hexagonal boron nitride flakes and the ionomer mixed at a weight ratio of 1:9 to 9:1.

8. The lithium metal secondary battery according to claim 1 , wherein the additive is used in an amount of 90 wt % to 93 wt % based on a total weight of the protective layer.

9. The lithium metal secondary battery according to claim 1 , wherein the hexagonal boron nitride flakes have a size ranging from 500 nm to 1 μm.

10. A lithium metal secondary battery comprising:
a positive electrode;
a negative electrode;
a separator interposed between the positive electrode and the negative electrode,
wherein the positive electrode and/or negative electrode comprises a solid electrolyte, and
wherein the solid electrolyte comprises an additive, wherein the additive comprises a mixture of hexagonal boron nitride (BN) flakes with an ionomer comprising a sulfur (S)-containing anionic group and fluorine (F), and
wherein the sulfur (S)-containing anionic group is SO 4 2− .

11. The lithium metal secondary battery according to claim 10 , wherein the additive is added in the form of an additive mixture combined with the solid electrolyte.

12. The lithium metal secondary battery according to claim 11 , wherein the solid electrolyte comprises at least one selected from the group consisting of a polymer solid electrolyte, polymer gel electrolyte, sulfide-based solid electrolyte and an oxide-based solid electrolyte.

Assignees

• Lg Energy Solution Ltd

Inventors

• Yoon Jong-Keon
• Park Sol-Ji
• Yun Hyun-Woong
• Ahn Kyoung-Ho
• Hah Hoe-Jin

Classifications

• H01M4/628 Primary

  Inhibitors, e.g. gassing inhibitors, corrosion inhibitors · CPC title

• C08G61/04

  only aliphatic carbon atoms · CPC title

• C08K3/38

  Boron-containing compounds · CPC title

• C08K7/00

  Use of ingredients characterised by shape · CPC title

• H01M4/366

  as layered products · CPC title