All-solid secondary battery and method of manufacturing the same

Patent metadata

Field	Value
Publication number	US-12191444-B2
Application number	US-202117376243-A
Country	US
Kind code	B2
Filing date	Jul 15, 2021
Priority date	Aug 6, 2020
Publication date	Jan 7, 2025
Grant date	Jan 7, 2025

Abstract

An all-solid secondary battery including: a cathode layer including a cathode active material layer; an anode layer; and a solid electrolyte layer between the cathode layer and the anode layer, and the solid electrolyte layer including a solid electrolyte, wherein the anode layer includes an anode current collector, a first anode active material layer in contact with the solid electrolyte layer, and a second anode active material layer between the anode current collector and the first anode active material layer, wherein the first anode active material layer is a lithium-containing first metal layer, wherein the second anode active material layer includes a carbon-containing anode active material or a carbon-containing anode active material and a second metal, and wherein a surface of the solid electrolyte layer adjacent to the first anode active material layer has a porosity of 40 percent or less.

First claim

What is claimed is:

1. An all-solid secondary battery comprising:
a cathode layer comprising a cathode active material layer;
an anode layer; and
a solid electrolyte layer between the cathode layer and the anode layer, the solid electrolyte layer comprising a solid electrolyte,
wherein the anode layer comprises
an anode current collector,
a first anode active material layer in contact with the solid electrolyte layer, and
a second anode active material layer between the anode current collector and the first anode active material layer,

wherein the first anode active material layer is a lithium-containing first metal layer comprising lithium and a first metal,
wherein the second anode active material layer comprises
a carbon-containing anode active material, or
a carbon-containing anode active material and a second metal, and

wherein
the solid electrolyte layer has an outermost surface adjacent to the first anode active material layer and an opposite second surface adjacent to the cathode layer, the solid electrolyte layer having a porous portion extending from the outermost surface in a direction towards the opposite second surface, and the porous portion having a porosity of 1 percent to 20 percent, and
the first metal of the lithium-containing first metal layer is present in a pore of the porous portion of the solid electrolyte layer and has a particle size of about 10 nanometers to about 900 nanometers,
wherein, the solid electrolyte layer comprises lithium, and a content of lithium of the solid electrolyte layer in an area within a 1 micrometer distance from the outermost surface of the solid electrolyte layer adjacent to the first anode active material layer is depleted by about 5 atomic percent to about 20 atomic percent, based on a total lithium content of the solid electrolyte.

2. The all-solid secondary battery of claim 1 , a thickness of the porous portion of the solid electrolyte layer is about 1% to about 50% of the total thickness of the solid electrolyte layer extending from the outermost surface of the solid electrolyte layer.

3. The all-solid secondary battery of claim 2 , wherein the porous portion of the solid electrolyte layer is an area within about 1 micrometer from the outermost surface of the solid electrolyte layer.

4. The all-solid secondary battery of claim 1 , wherein the first metal and the second metal independently comprise indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, silver, zinc, or a combination thereof.

5. The all-solid secondary battery of claim 1 , wherein the lithium-containing first metal layer comprises a lithium-first metal alloy interlayer adjacent to the solid electrolyte layer and a first metal layer adjacent to the lithium-first metal alloy interlayer, and
wherein the lithium-first metal alloy interlayer has a thickness of 7 micrometers or less.

6. The all-solid secondary battery of claim 5 , wherein the first metal in the lithium-first metal interlayer comprises indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, silver, zinc, or a combination thereof.

7. The all-solid secondary battery of claim 1 , wherein, the first metal is uniformly dispersed in porous portion of the solid electrolyte layer.

8. The all-solid secondary battery of claim 1 , wherein the first anode active material layer further comprises a third metal in an area adjacent to the solid electrolyte layer, and
a content of the third metal is 30 atomic percent or less, based on the total atomic weight of the first anode active material layer.

9. The all-solid secondary battery of claim 8 , wherein the third metal comprises lanthanum, titanium, zirconium, or a combination thereof.

10. The all-solid secondary battery of claim 1 , wherein the first anode active material layer does not comprise a binder, and
the second anode active material layer comprises a binder.

11. The all-solid secondary battery of claim 1 , wherein the carbon-containing anode active material has a particle form, and
the carbon-containing anode active material has a particle size of about 5 micrometers or less.

12. The all-solid secondary battery of claim 1 , wherein the carbon-containing anode active material comprises amorphous carbon.

13. The all-solid secondary battery of claim 1 , wherein
the second anode active material layer comprises a composite comprising first particles comprising amorphous carbon and second particles comprising a second metal, and
wherein a content of the second particles is about 1 weight percent to about 60 weight percent based on a total weight of the composite.

14. The all-solid secondary battery of claim 1 , wherein each of a thickness of the first anode active material layer and a thickness of the second anode active material layer are 50% or less of a thickness of the cathode active material layer, and
wherein the thickness of the first anode active material layer is about 1 micrometer to about 10 micrometers, and the thickness of the second anode active material layer is about 10 nanometers to about 10 micrometers.

15. The all-solid secondary battery of claim 1 , wherein a thickness of the first anode active material layer is less than a thickness of the second anode active material layer.

16. The all-solid secondary battery of claim 1 , further comprising a third anode active material layer
between the anode current collector and the second anode active material layer, or
between the first anode active material layer and the second anode active material layer, or
between the anode current collector and the second anode active material layer and between the first anode active material layer and the second anode active material layer,
wherein the third anode active material layer is a metal layer comprising lithium or a lithium alloy.

17. The all-solid secondary battery of claim 1 , wherein
the anode current collector, the first anode active material layer, the second anode active material layer, and an area therebetween are free of lithium, and do not comprise lithium in an initial state or a post-discharge state.

18. The all-solid secondary battery of claim 1 , wherein the solid electrolyte is an oxide-containing solid electrolyte or a sulfide-containing solid electrolyte.

19. The all-solid secondary battery of claim 18 , wherein the oxide-containing solid electrolyte comprises Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 wherein 0<x<2, 0≤y<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 2 O, LiOH, Li 2 CO 3 , LiAlO 2 , Li 2 O—Al 2 O—SiO 2 —P 2 O 5 —TiO 2 —GeO 2 , Li 3+x La 3 M 2 O 12 wherein M is Te, Nb, or Zr, and 0≤x≤10, or a combination thereof.

20. The all-solid secondary battery of claim 18 , wherein the oxide-containing solid electrolyte is a garnet-type solid electrolyte comprising Li 7 La 3 Zr 2 O 12 , Li 3+x La 3 Zr 2−a M a O 12 wherein M=Ga, W, Nb, Ta, or Al and 0≤x≤10, or a combination thereof.

21. The all-solid secondary battery of claim 18 , wherein the sulfide-containing solid electrolyte comprises Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —LiX wherein X is a halogen, Li z S—P 2 S 5 —Li 2 O, Li 2 S—P 2 S 5 —Li 2 O—LiI, Li 2 S—SiS 2 , Li 2 S—SiS 2 —LiI, Li

Assignees

• Samsung Electronics Co Ltd
• Corning Inc

Inventors

• Kim Jusik
• Lee Myungjin
• Kim Sewon
• Badding Michael Edward
• Chang Jaemyung
• Song Zhen

Classifications

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/133

  Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M2300/0071

  Oxides · CPC title