All-solid secondary battery and method of manufacturing all-solid secondary battery

Patent metadata

Field	Value
Publication number	US-2021119203-A1
Application number	US-202017075059-A
Country	US
Kind code	A1
Filing date	Oct 20, 2020
Priority date	Oct 22, 2019
Publication date	Apr 22, 2021
Grant date	—

Abstract

An all-solid secondary battery including: a cathode layer including a cathode active material; an anode layer; and a solid electrolyte layer including a solid electrolyte disposed between the cathode layer and the anode layer, 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 disposed between the anode current collector and the first anode active material layer, wherein the first anode active material layer includes a first metal and has a lithium-ion reduction potential greater than a reduction potential of the solid electrolyte, and wherein the second anode active material layer includes a second metal, and a solid solubility of lithium (Li) in the second metal is greater than a solid solubility of lithium in the first metal.

First claim

What is claimed is:

1 . An all-solid secondary battery comprising:
a cathode layer comprising a cathode active material; an anode layer; and a solid electrolyte layer comprising a solid electrolyte and disposed between the cathode layer and the anode layer, 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 disposed between the anode current collector and the first anode active material layer,
wherein the first anode active material layer comprises
a first metal and has a lithium-ion reduction potential greater than a reduction potential of the solid electrolyte, and
wherein the second anode active material layer comprises a second metal, and a solid solubility of lithium in the second metal is greater than a solid solubility of lithium in the first metal.

2 . The all-solid secondary battery of claim 1 , wherein the first anode active material layer has a lithium-ion reduction potential of about 0.05 volts to about 2.5 volt with respect to lithium.

3 . The all-solid secondary battery of claim 1 , wherein
a lithium ion diffusivity at 25° C. of the first anode active material layer is equal to or greater than a lithium ion diffusivity at 25° C. of the second anode active material layer, and the first anode active material layer has a lithium ion diffusivity at 25° C. of about 1×10 −16 square centimeters per second to about 1×10 −3 square centimeters per second.

4 . The all-solid secondary battery of claim 1 , wherein a difference between the solid solubility of lithium in the second metal and the solid solubility of lithium in the first metal is about 10 atomic percent or greater.

5 . The all-solid secondary battery of claim 1 , wherein the second metal has a Mohs hardness equal to or greater than a Mohs hardness of the first metal, and
the Mohs hardness of the first metal is equal to or greater than a Mohs hardness of lithium.

6 . The all-solid secondary battery of claim 1 , wherein the first metal comprises at least one of indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, zinc, gold, platinum, palladium, iron, cobalt, chromium, cesium, cerium or lanthanum.

7 . The all-solid secondary battery of claim 1 , wherein the second metal comprises at least one of silver, gold, platinum, palladium, silicon, aluminum, bismuth, magnesium, tin, or zinc.

8 . The all-solid secondary battery of claim 1 , wherein at least one of the first anode active material layer and the second anode active material layer comprises an anode active material in a form of a film.

9 . The all-solid secondary battery of claim 8 , wherein
the first anode active material layer comprises at least one of the first metal, lithium, or an alloy of the first metal and lithium, and the second anode active material layer comprises at least one of a second metal, lithium, or an alloy of the second metal and lithium.

10 . The all-solid secondary battery of claim 1 , wherein
a thickness of at least one of the first anode active material layer and the second anode active material layer is about 50% or less of a thickness of the cathode active material layer, and the thickness of the at least one of the first anode active material layer and the second anode active material layer is about 10 nanometers to about 100 micrometers.

11 . The all-solid secondary battery of claim 10 , wherein the thickness of the at least one of the first anode active material layer and the second anode active material layer is about 10 nanometers to about 500 nanometers.

12 . The all-solid secondary battery of claim 1 , wherein at least one of the first anode active material layer and the second anode active material layer comprises
an anode active material in a form of a plurality of particles, and a binder

13 . The all-solid secondary battery of claim 12 , wherein the plurality of particle has an average particle diameter of about 4 micrometers or less.

14 . The all-solid secondary battery of claim 12 ,
wherein the anode active material in the form of particles comprises at least one of amorphous carbon, a metal, or a metalloid, and wherein the first metal and the second metal each independently comprise the metal or the metalloid.

15 . The all-solid secondary battery of claim 14 , wherein the anode active material in the form of particles comprises
a mixture of first particles consisting of amorphous carbon and second particles consisting of the metal, the metalloid, or a combination thereof, and an amount of the second particles is about 8 weight percent to about 60 weight percent, based on a total weight of the mixture.

16 . The all-solid secondary battery of claim 12 , wherein at least one of the first anode active material layer and the second anode active material layer has a thickness of about 1 micrometer to about 20 micrometers.

17 . The all-solid secondary battery of claim 1 , further comprising a third anode active material layer disposed 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 solid electrolyte layer and the first anode active material layer and
wherein the third anode active material layer comprises lithium or a lithium alloy.

18 . The all-solid secondary battery of claim 17 , wherein a thickness of the first anode active material layer is about 5 percent to about 150 percent of a thickness of the third anode active material layer, wherein the thickness of the first anode active material layer and the thickness of the third anode active material layer are determined in a charged state.

19 . 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 regions therebetween are each a lithium free region which do not include lithium in an initial state or in a post discharge state of the all-solid secondary battery.

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

21 . The all-solid secondary battery of claim 20 , wherein the oxide-based solid electrolyte is at least one of 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 x Ti 1−x )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 , HfO 2 , SrTiO 3 , SnO 2 , CeO 2 , Na 2 O, MgO, NiO, CaO, BaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , 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 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 , or Li 3+x La 3 M 2 O 12 wherein M is Te, Nb, or Zr, and x is an integer from 1 to 10.

22 . The all-solid secondary battery of claim 20 , wherein the oxide solid electrolyte comprises at least one of Li 7 La 3 Zr 2 O 12 or Li 3+x La 3 Zr 2−a M a O 12 , wherein M is Ga, W, Nb, Ta, or Al, and x is an integer from 1 to 10 and 0≤a<2.

23 . The all-solid secondary battery of claim 20 , wherein the sulfide solid elec

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kim Sewon
• Kim Jusik
• Gwon Hyeokjo
• Kim Ryounghee
• Kim Hyunseok
• Jung Sungkyun
• Jung Changhoon

Classifications

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M4/386

  Silicon or alloys based on silicon · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M4/405

  Alloys based on lithium · CPC title