Solid electrolyte, method of preparing the same, and secondary battery including the same

Patent metadata

Field	Value
Publication number	US-11949065-B2
Application number	US-202117238488-A
Country	US
Kind code	B2
Filing date	Apr 23, 2021
Priority date	Sep 6, 2018
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

A solid electrolyte including an inorganic lithium ion conductive film and a porous layer on a surface of the inorganic lithium ion conductive film, wherein the porous layer includes a first porous layer and a second porous layer, and the second porous layer is disposed between the inorganic lithium ion conductive film and the first porous layer, and wherein the first porous layer has a size greater which is than a pore size of the second porous layer.

First claim

What is claimed is:

1. A solid electrolyte comprising:
an inorganic lithium ion conductive film; and
a porous layer on a surface of the inorganic lithium ion conductive film,
wherein the porous layer has an inner surface facing the inorganic lithium ion conductive film and an opposite outer surface, and an amount of protons on the outer surface of the porous layer is greater than an amount of protons inside the porous layer,
wherein the porous layer comprises a first porous layer and a second porous layer, and the second porous layer is disposed between the inorganic lithium ion conductive film and the first porous layer,
wherein the first porous layer has a pore size which is greater than a pore size of the second porous layer, and
wherein the first porous layer comprises a first inorganic lithium ion conductor substituted with about 2% to about 100% protons, and the second porous layer solid electrolyte comprises a second inorganic lithium ion conductor substituted with about 0.01% to about 20% protons, based on the total number of protons and lithium ions.

2. The solid electrolyte of claim 1 , wherein the porous layer has a total thickness and density to be impermeable to a liquid.

3. The solid electrolyte of claim 1 , wherein the porous layer of the solid electrolyte has a thickness of about 5% to about 95% of the total thickness of the solid electrolyte.

4. The solid electrolyte of claim 1 , wherein an average pore size of a pore in the porous layer is from about 0.1 micrometer to about 1,000 micrometers.

5. The solid electrolyte of claim 1 , wherein a pore in the first porous layer has an average pore size of about 10 micrometers to about 500 micrometers, and a pore in the second porous layer has an average pore size of about 0.1 micrometer to about micrometers.

6. The solid electrolyte of claim 1 , wherein at least a portion of the solid electrolyte comprises an inorganic lithium ion conductor comprising lithium, and a portion of the lithium is substituted by a proton.

7. The solid electrolyte of claim 6 , wherein an amount of protons in the porous layer is from about 0.01 mole percent to about 50 mole percent based on a total number of protons and lithium ions in the porous layer.

8. The solid electrolyte of claim 1 , wherein the porous layer is a product obtained by:
acid-treating the inorganic lithium ion conductive film with an acid having a concentration of greater than or equal to about 0.1 molar and less than or equal to about 5 molar.

9. The solid electrolyte of claim 8 , wherein the concentration of the acid is from about 0.5 molar to about 4.5 molar.

10. The solid electrolyte of claim 1 , wherein the porous layer is a product obtained by:
forming a multilayer film comprising two or more layers on an inorganic lithium ion conductive film; and
heat-treating the multilayer film,
wherein the forming of the multilayer film comprises coating a first composition comprising a pore former on a surface of the inorganic lithium ion conductive film and coating a second composition comprising a pore former on the first composition, wherein the amount of the pore former in the first composition is different from the amount of the pore former in the second composition.

11. The solid electrolyte of claim 1 , wherein a lattice constant of the porous layer as measured by X-ray diffraction is greater than a lattice constant of the remaining area of the solid electrolyte excluding the porous layer by about 0.005 angstrom to about 0.1 angstrom, and
an average grain size of the porous layer is greater than an average grain size of the remaining area of the solid electrolyte excluding the porous layer by twice or more.

12. The solid electrolyte of claim 1 , wherein the inorganic lithium ion conductive film comprises at least one of a garnet compound, an argyrodite compound, a lithium super-ion-conductor compound, a Li nitride, a Li hydride, a perovskite, or a Li halide.

13. The solid electrolyte of claim 1 , wherein the inorganic lithium ion conductive film comprises at least one of Li 3+x La 3 M 2 O 12 wherein 0≤x≤5 and M is W, Ta, Te, Nb, Zr or a combination thereof, Li 3+x La 3 M 2 O 12 wherein 0≤x≤5 and M is W, Ta, Te, Nb, Zr 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,Ga) x (Ti,Ge) 2−x Si y P 3−y O 12 wherein 0≤x≤1 and 0≤y≤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, Li x Si y S z wherein 0≤x<3, 0<y<2, and 0<z<4, Li x P y S z 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, Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 ceramic, 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 , LiGe 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , Li 2 NH, Li 3 (NH 2 ) 2 I, LiBH 4 , LiAlH 4 , LiNH 2 , Li 0.34 La 0.5 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, or Li 5.39 Ga 0.5+δ La 3 Zr 1.7 W 0.3 O 12 wherein 0≤δ<1.11.

14. The solid electrolyte of claim 1 , wherein the inorganic lithium ion conductive film comprises at least one of 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   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 or aluminum,
in Formulas 1 and 1a, M 2 comprises at least one of calcium, strontium, cesium, or barium,
M 3 comprises at least one of aluminum, tungsten, niobium, or tantalum, and
0≤x<3, 0≤a≤3, and 0≤b<2.

15. The solid electrolyte of claim 1 , wherein the inorganic lithium ion conductive film comprises at least one of Li 7 La 3 Zr 2 O 12 , Li 6.4 La 3 Zr 1.7 W 0.3 O 12 , Li 6.5 La 3 Zr 1.5 Ta 0.3 O 12 , Li 7 La 3 Zr 1.7 W 0.3 O 12 , Li 4.9 La 2.5 Ca 0.5 Zr 1.7 Nb 0.3 O 12 , Li 4.9 Ga 2.1 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 1.61 La 3 Zr 1.7 W 0.3 O 12 .

16. The solid electrolyte of claim 1 , wherein a surface of the solid electrolyte comprises Li 7−x H x La 3 Zr 2−y M y O 12 wherein 0.1≤x≤7, 0≤y≤2, and M is at least one of W, Ta, Te, or Nb, and the interior of the solid electrolyte comprises Li 7−x H x La 3 Zr 2−y M y O 12 wherein 0≤x≤6.5, 0≤y≤2, and M is at least one of W, Ta, Te, or Nb.

17. The solid electrolyte of claim 1 , wherein the first porous layer defines a surface of the solid electrolyte and has a porosity of about 5% to about 80%, and the second porous layer has a porosity of about 1% to about 50%.

18. The solid electrolyte of claim 1 , wherein the first porous layer comprises a lithium ion conductor substituted with Li 7−x H x La 3 Zr 2 O 12 wherein 0.1≤x≤7 and the second porous layer comprises Li 7−x H x

Assignees

• Samsung Electronics Co Ltd
• Corning Inc

Inventors

• Kim Jusik
• Kim Sewon
• Kim Hyunseok
• Badding Michael Edward
• Song Zhen
• Thomas-Alyea Karen E
• Miara Lincoln James
• Im Dongmin

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M2300/0094

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

• H01M10/0525

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

• H01M50/403

  Manufacturing processes of separators, membranes or diaphragms · CPC title