Solid electrolyte, method of preparing the same, and lithium battery including the solid electrolyte

Patent metadata

Field	Value
Publication number	US-12476277-B2
Application number	US-202217666804-A
Country	US
Kind code	B2
Filing date	Feb 8, 2022
Priority date	Aug 4, 2017
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

A solid electrolyte including: a lithium ion inorganic conductive layer; and an amorphous phase on a surface of the lithium ion inorganic conductive layer, wherein the amorphous phase is an irradiation product of the lithium ion inorganic conductive layer. Also, the method of preparing the same, and a lithium battery including the solid electrolyte.

First claim

What is claimed is:

1 . A solid electrolyte, comprising:
a lithium ion inorganic conductive layer; an amorphous phase film on the lithium ion inorganic conductive layer, wherein a surface of the amorphous phase film includes a line pattern in a form of a mesh, a semi-crystalline film situated between the lithium ion inorganic conductive layer and the mesh-patterned amorphous phase film; and a crystalline phase situated between the semi-crystalline film and the line patterned mesh-patterned amorphous phase film, wherein the mesh-pattern has a pattern size of about 10 μm to about 10,000 μm, and the pattern width is in a range of about 1 μm to about 150 μm.

2 . The solid electrolyte of claim 1 , wherein the mesh-patterned amorphous phase film has a thickness of about 5 nanometers to about 5 micrometers, the semi-crystalline film has a thickness of about 2 nanometers to about 3 micrometers, and a thickness ratio of the mesh-patterned amorphous phase film to the semi-crystalline film is in a range of about 1:0.2 to about 1:0.8.

3 . The solid electrolyte of claim 1 , wherein the crystalline phase is in the form of a crystalline film.

4 . The solid electrolyte of claim 1 , wherein the mesh-patterned amorphous phase film has a surface area of about 200 percent to about 500 percent greater than a surface area of the lithium ion inorganic conductive layer beneath the mesh-patternedline amorphous phase film.

5 . The solid electrolyte of claim 1 , further comprising at least one of a ceramic layer or a ceramic glass layer on an unpatterned surface of the lithium ion inorganic conductive layer.

6 . The solid electrolyte of claim 1 , wherein the lithium ion inorganic conductive layer comprises at least one of a garnet compound, an argyrodite compound, a lithium super ionic conductor, a sodium super ionic conductor, lithium nitride, lithium hydride, a compound having a perovskite structure, or a lithium halide.

7 . The solid electrolyte of claim 1 , wherein the lithium ion inorganic conductive layer comprises at least one of:
a garnet ceramic of the formula Li 3+x La 3 M 2 O 12 wherein 0≤x≤5, and M is tellurium, niobium, or zirconium, 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 1−x Tix)O 3 wherein 0<x<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 glass of the formula Li x Si y S z glass wherein 0≤x<3, 0<y<2, and 0<z<4, a glass of the formula 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≤x≤1, Li 1+z Al z Ge 2−z (PO 4 ) 3 wherein 0≤x≤1, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a (Li 2 O) a —(Al 2 O 3 ) b —(SiO 2 ) c —(P 2 O 5 ) a —(TiO 2 ) e —(GeO 2 ) f ceramic wherein 0≤a≤1, 0≤b≤1, 0≤c≤1, 0≤d≤1, 0≤e≤1, and 0≤f≤1, Li 10 GeP 2 S 12 , Li 3 PS 4 , Li 6 PS 5 Br, Li 6 PS 5 Cl, Li 7 PS 5 , Li 6 PS 5 I, LiTi 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , Li 2 NH 2 , 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 , and Li 2 CdI 4 .

8 . The solid electrolyte of claim 7 , wherein a crystallinity of the lithium ion inorganic conductive layer increases in a direction away from the mesh-patterned amorphous phase film.

9 . The solid electrolyte of claim 1 , wherein the lithium ion inorganic conductive layer comprises at least one compound selected from a compound of Formula 1 or a compound of Formula 1a:
Formula 1
Li 7-x M 1 x La 3-a M 2 a Zr 2-b M 3 b O 12 , and   Formula 1

Li 7-x La 3-a M 2 a Zr 2-b M 3 b O 12 ,   Formula 1a

wherein, in Formula 1, M 1 comprises at least one of gallium and aluminum, in Formulas 1 and 1a, M 2 comprises at least one of calcium, strontium, cesium, and barium, M 3 comprises at least one of aluminum, tungsten, niobium, and tantalum, and 0≤x<3, 0≤a≤3, and 0≤b<2.

10 . The solid electrolyte of claim 9 , wherein the crystalline phase is in a form of a crystalline film,
wherein if present, the M 1 , M 2 , and M 3 of Formulas 1 and 1a are dopants, and wherein a total content of the dopant in the mesh-patterned amorphous phase film is less than a total content of the dopant in the crystalline film.

11 . The solid electrolyte of claim 9 , wherein at least one of M 1 , M 2 , or M 3 of Formulas 1 and 1 a is present and are dopants, and
wherein a total content of the dopant in the amorphous phase is equal to or less than 1 mole percent, based on 100 mole percent of the mesh-patterned amorphous phase film.

12 . The solid electrolyte of claim 9 , wherein the compound of Formula 1 is at least one of Li 4.9 La 2.5 Ca 0.5 Zr 1.7 Nb 0.3 O 12 , Li 4.9 Ga 0.5+δ La 3 Zr 1.7 W 0.3 O 12 wherein 0≤δ≤1.6, Li 6.4 La 3 Zr 1.7 W 0.3 O 12 , Li 7 La 3 Zr 1.5 W 0.5 O 12 , Li 7 La 2.75 Ca 0.25 Zr 1.75 Nb 0.25 O 12 , Li 7 La 3 Zr 1.5 Nb 0.5 O 12 , Li 7 La 3 Zr 1.5 Ta 0.5 O 12 , Li 6.272 La 3 Zr 1.7 W 0.3 O 12 , or Li 5.39 Ga 0.5+δ La 3 Zr 1.7 W0.3O 12 wherein 03≤δ≤1.1.

13 . The solid electrolyte of claim 1 , wherein the lithium ion inorganic conductive layer is a crystalline film having a crystal grain boundary, and
wherein a thickness ratio of the lithium ion inorganic conductive layer to the mesh-patterned amorphous phase film is from 1:0.001 to 1:0.2.

14 . The solid electrolyte of claim 1 , wherein ion conductivity at 60° C. of the solid electrolyte is in a range of about 5×10 -4 Siemens per centimeter or greater.

15 . The solid electrolyte of claim 1 , wherein the solid electrolyte has ionic conductivity at 25° C. of 1×10 -7 Siemens per centimeter to 5×10 -3 Siemens per centimeter.

16 . The solid electrolyte of claim 1 , wherein the solid electrolyte is a liquid-impermeable layer having a porosity of 30% or less, and a thickness of the solid electrolyte is about 1 micrometer to about 300 micrometers.

17 . The solid electrolyte of claim 1 , wherein the mesh-patterned amorphous film comprises a plurality of grooves that forms the mesh pattern.

18 . The solid electrolyte of claim 17 , wherein a depth of a groove of the plurality of grooves is in a range from about 0.1 μm to about 20 μm, and a width of the groove of the plurality of grooves is about 1-10 μm to about 200-100 μm.

19 . The solid electrolyte of claim 1 , wherein the mesh-patterned amorphous phase film is a product of ultraviolet laser irradiation of the lithium ion inorganic conductive layer, and the semi-crystalline film is a product of melt quenching.

20 . The solid electrolyte of claim 1 , wherein the semi-crystalline film is a product of melt quenching.

21 . The solid electrolyte of claim 1 , wherein a surface of the mesh-patterned amorphous phase film does not comprise a grain boundary.

22 . The solid electrolyte of claim 1 , wherein the lithium ion inorganic conductive layer comprises at least one compound selected from a compound of Formula 1 and a compound of Formula 1a:
Li 7-x M 1 x La 3-a M 2 a Zr 2-b M 3 b O 12 , and   Formul

Assignees

• Samsung Electronics Co Ltd
• Corning Inc

Inventors

• Kim Jusik
• Badding Michael Edward
• Kim Hyunseok
• Song Zhen
• Yu Taehwan

Classifications

• H01M50/431

  Inorganic material · CPC title

• H01M50/403

  Manufacturing processes of separators, membranes or diaphragms · CPC title

• H01M2300/0094

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

• H01M2300/0077

  based on zirconium oxide · CPC title

• H01M2300/0068

  inorganic · CPC title