Solid electrolyte, preparation method thereof, lithium air battery including the solid electrolyte, and electrochemical device including the solid electrolyte

Patent metadata

Field	Value
Publication number	US-12362386-B2
Application number	US-202217877605-A
Country	US
Kind code	B2
Filing date	Jul 29, 2022
Priority date	Dec 17, 2021
Publication date	Jul 15, 2025
Grant date	Jul 15, 2025

Abstract

A solid electrolyte includes: a first electrolyte layer including an inorganic lithium ion conductor; and a second electrolyte layer disposed on at least one side of the first electrolyte layer and including a compound represented by Formula 1

Li 1−3x+4y (Hf a M 1−a ) 2−y (PO 4−x Q x ) 3   Formula 1

wherein in Formula 1, M is at least one of a monovalent to a hexavalent element, wherein 0<a≤1, 0≤x<⅓, and 0≤y<2, and Q is F, Cl, Br, I, a pseudohalogen, or a combination thereof.

First claim

What is claimed is:

1. A solid electrolyte comprising:
a first electrolyte layer comprising an inorganic lithium ion conductor; and
a second electrolyte layer disposed on at least one side of the first electrolyte layer and comprising a compound represented by Formula 1
Li 1−3x+4y (Hf a M 1−a ) 2−y (PO 4−x Q x ) 3   Formula 1

wherein, in Formula 1, M is at least one of a monovalent to a hexavalent element, wherein 0<a≤1, 0≤x<⅓, and 0≤y<2, and Q is F, Cl, Br, I, a pseudohalogen, or a combination thereof.

2. The solid electrolyte of claim 1 , wherein in Formula 1, a is 0.7 to 0.98, or a is 1.

3. The solid electrolyte of claim 1 , wherein in Formula 1, x is 0.01 to 0.05.

4. The solid electrolyte of claim 1 , wherein the compound represented by Formula 1 is a compound represented by Formula 2, a compound represented by Formula 3, or a combination thereof
Li 1−3x (Hf a M1 1−a ) 2 (PO 4−x Q x ) 3   Formula 2

wherein, in Formula 2, M1 is a tetravalent element, wherein 0<a≤1 and 0≤x<⅓, and Q is F, Cl, Br, I, or a combination thereof, or
Li 1+4y (Hf a M2 1−a ) 2−y (PO 4 ) 3   Formula 3

wherein, in Formula 3, M2 is a tetravalent element and is Ti, Zr, Ge, Sn, or a combination thereof, and 0<a≤1 and 0≤y<2.

5. The solid electrolyte of claim 1 , wherein the compound represented by Formula 1 is a compound represented by Formula 4, a compound represented by Formula 5, or a combination thereof
Li 1−3x Hf 2 (PO 4−x Q x ) 3   Formula 4

wherein, in Formula 4, 0≤x<⅓, and Q is F, Cl, Br, I, or a combination thereof, or
Li 1+4y Hf 2−y (PO 4 ) 3   Formula 5

wherein, in Formula 5, 0≤y<2.

6. The solid electrolyte of claim 1 ,
wherein the first electrolyte layer comprises a first side and an opposite second side, wherein the second electrolyte layer is disposed on the first side of the first electrolyte layer, and
wherein the solid electrolyte further comprises a third electrolyte layer disposed on the second side of the first electrolyte layer.

7. The solid electrolyte of claim 1 , wherein the compound represented by Formula 1 is Li 0.9 Hf 2 P 3 O 11.9 F 0.1 , Li 0.9 Hf 2 P 3 O 11.9 Cl 0.1 , Li 1.4 Hf 1.9 P 3 O 12 , Li 0.8 Hf 2 P 3 O 11.8 Cl 0.2 , Li 0.8 Hf 2 P 3 O 11.8 F 0.1 Cl 0.1 , Li 0.9 Hf 1.8 Zr 0.2 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.8 Sn 0.2 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.9 Sn 0.1 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.9 Ge 0.1 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.8 Ti 0.2 P 3 O 11.9 F 0.1 , Li 0.8 Hf 2 P 3 O 11.8 F 0.2 , Li 0.8 Hf 2 P 3 O 11.8 Cl 0.2 , Li 0.9 Hf 1.9 Y 0.1 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.9 Y 0.1 P 3 O 11.9 Cl 0.1 , Li 0.8 Hf 2 P 3 O 11.8 Br 0.2 , Li 0.8 Hf 2 P 3 O 11.8 Br 0.1 F 0.1 , Li 0.8 Hf 2 P 3 O 11.8 Br 0.1 Cl 0.1 , Li 0.9 HF 1.9 Y 0.1 P 3 O 11.9 Br 0.1 , Li 0.9 Hf 1.9 Y 0.1 P 3 O 11.9 Br 0.05 F 0.05 , Li 0.9 Hf 1.9 Y 0.1 P 3 O 11.9 Br 0.05 Cl 0.05 , Li 0.9 Hf 1.9 Al 0.1 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.9 Al 0.1 P 3 O 11.9 Br 0.1 , Li 0.9 Hf 1.9 Al 0.1 P 3 O 11.9 F 0.05 Br 0.05 , Li 0.9 Hf 1.9 Al 0.1 P 3 O 11.9 Cl 0.1 , Li 0.9 Hf 1.9 Al 0.1 P 3 O 11.9 Cl 0.05 Br 0.05 , Li 0.9 Hf 1.9 La 0.1 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.9 La 0.1 P 3 O 11.9 Br 0.1 , Li 0.9 Hf 1.9 La 0.1 P 3 O 11.9 F 0.05 Br 0.05 , Li 0.9 Hf 1.9 La 0.1 P 3 O 11.9 Cl 0.05 Br 0.05 , Li 0.9 Hf 1.9 La 0.1 P 3 O 11.9 Cl 0.1 , Li 0.9 Hf 1.9 Gd 0.1 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.9 Gd 0.1 P 3 O 11.9 F 0.05 Br 0.05 , Li 0.9 Hf 1.9 Gd 0.1 P 3 O 11.9 Cl 0.05 Br 0.05 , Li 0.9 Hf 1.9 Gd 0.1 P 3 O 11.9 Cl 0.1 , Li 0.9 Hf 1.9 Y 0.1 P 3 O 11.9 F 0.05 Cl 0.05 , Li 0.8 Ti 2 P 3 O 11.8 F 0.1 Cl 0.1 , Li 0.9 Ti 1.9 Y 0.1 P 3 O 11.9 F 0.05 Cl 0.05 , Li 0.8 Zr 2 P 3 O 11.8 F 0.1 Cl 0.1 , Li 0.9 Zr 1.9 Y 0.1 P 3 O 11.9 F 0.05 Cl 0.05 , Li 0.9 Hf 1.9 Zr 0.1 P 3 O 11.9 F 0.1 , Li 0.9 Hf 1.9 Ti 0.1 P 3 O 11.9 F 0.1 , or a combination thereof.

8. The solid electrolyte of claim 1 , wherein the first electrolyte layer has a thickness of about 5 micrometers to about 800 micrometers.

9. The solid electrolyte of claim 1 , wherein the second electrolyte layer has a thickness of about 500 nanometers to about 100 micrometers.

10. The solid electrolyte of claim 1 , wherein the second electrolyte layer has a thickness which is about 10 percent to about 30 percent less than a thickness of the first electrolyte layer.

11. The solid electrolyte of claim 1 , wherein the inorganic lithium ion conductor is a garnet-type compound, an argyrodite-type compound, a lithium super-ionic-conductor compound, a sodium super-ionic-conductor compound, a lithium nitride, a lithium hydride, a perovskite, a lithium halide, or a combination thereof.

12. The solid electrolyte of claim 1 , wherein the inorganic lithium ion conductor comprises a garnet-type ceramic of the formula Li 3+x La 3 M 2 O 12 wherein (0≤x≤5, M is W, Ta, Te, Nb, Zr, or a combination thereof, a doped-garnet type ceramic of the formula Li 3+x La 3 M 2 O 12 wherein (0≤x≤5, M is W, Ta, Te, Nb, Zr, or a combination thereof, and further comprising a dopant, wherein the dopant is Ge, Ta, Nb, Al, Ga, Sc, or a combination thereof, Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0≤x<2 and 0≤y<3, BaTiO 3 , Pb(Zr a Ti 1−a )O 3 wherein 0≤a≤1, Pb 1−x La x Zr 1−y Ti y O 3 wherein 0≤x<1 and 0≤y<1, Pb(Mg 1/3 Nb 2/3 )O 3 —PbTiO 3 , Li 3 PO 4 , Li x Ti y (PO 4 ) 3 wherein 0<x<2 and 0<y<3, Li x Al y Ti z (PO 4 ) 3 wherein 0<x<2, 0<y<1, and 0<z<3, Li 1+x+y (Al a Ga 1−a ) x (Ti b Ge 1−b ) 2−x Si y P 3−y O 12 wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0<b≤1, Li x La y TiO 3 wherein 0<x<2 and 0<y<3, Li x Ge y P z S w , wherein 0<x<4, 0<y<1, 0<z<1 and 0<w<5, Li x N y wherein 0<x<4 and 0<y<2, a Li x Si y S z glass wherein 0≤x<3, 0<y<2 and 0<z<4, a Li x P y S z glass wherein 0≤x<3, 0<y<3 and 0<z<7, Li 3x La 2/3−x TiO 3 wherein 0≤x≤⅙, Li 1+y Al y Ti 2−y (PO 4 ) 3 wherein 0≤y≤1, Li 1+z Al z Ge 2−z (PO 4 ) 3 wherein 0≤z≤1, LiO, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a LiO—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 ceramics, Li 7 La 3 Zr 2 O 12 , Li 10 GeP 2 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4 , Li 3 PS 4 , Li 6 PS 5 Br, Li 6 PS 5 Cl, Li 7 PS 5 , Li 6 PS 5 I, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , LiTi 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , LiZr 2 PO 4 ) 3 , Li 3 (NH 2 ) 2 I, LiBH 4 , LiAlH 4 , LiNH 2 , Li 0.34 La 0.51 TiO 2.94 , LiSr 2 Ti 2 NbO 9 , Li 0.06 La 0.66 Ti 0.93 Al 0.03 O 3 , Li 0.34 Nd 0.55 TiO 3 , Li 2 CdCl 4 , Li 2 MgCl 4 , Li 2 ZnI 4 , Li 2 CdI 4 , Li 4.9 Ga 0.5+δ La 3 Zr 1.7 W 0.3 O 12 wherein 0≤δ≤1.6, Li 4.9 Ga 0.5+δ La 3 Zr 1.7 W 0.3 O 12 wherein 1.7≤δ≤2.5, Li 5.39 Ga 0.5+δ La 3 Zr 1.7 W 0.3 O 12 wherein 0≤δ≤1.11, or a combination thereof.

13. The solid electrolyte of claim 1 , wherein the solid electrolyte comprises a compound that is isostructural with a sodium super-ionic-conductor compound.

14. The solid electrolyte of claim 1 , wherein the first electrolyte layer comprises a phosphate having a titanium-containing compound which is isostructural with a sodium super-ionic-conductor compound.

15. The solid electrolyte of claim 1 , wherein the first electrolyte layer comprises Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0<x<2 and 0≤y<3.

16. The solid electrolyte of claim 1 , wherein the first electrolyte layer comprises Li 1−x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0<x<2 and 0≤y<3, and the second electrolyte layer comprises a compound represented by Formula 4, a compound represented by Formula 5, or a combination thereof
Li 1−3x Hf 2 (PO 4−x Q x ) 3   Formula 4

wherein in Formula 4, 0≤x<⅓, and Q is F, Cl, Br, I, or a combination thereof,
Li 1+4y Hf 2−y (PO 4 ) 3   Formula 5

wherein in Formula 5, 0≤y<2.

17. The solid electrolyte of claim 1 , wherein the solid electrolyte has an ion conductivity retention of

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kim Mokwon
• Lee Hyunpyo
• Ma Sangbok
• Park Jungock

Classifications

• H01M10/0525

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

• H01M2300/008

  Halides · CPC title

• H01M2300/0094

  in the form of layered products, e.g. coatings · CPC title

• H01B1/06

  mainly consisting of other non-metallic substances · CPC title

• H01M12/08

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title