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

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 the first metal 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,

wherein the first metal comprises indium,

wherein the second metal comprises at least one of silver, gold, platinum, palladium, silicon, aluminum, bismuth, magnesium, tin, or zinc,

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.

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 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.

4 . 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.

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

6 . 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.

7 . The all-solid secondary battery of claim 6 , 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.

8 . The all-solid secondary battery of claim 1 , wherein

a thickness of at least one of the first anode active material layer or 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 or the second anode active material layer is about 10 nanometers to about 100 micrometers.

9 . The all-solid secondary battery of claim 8 , wherein the thickness of the at least one of the first anode active material layer or the second anode active material layer is about 10 nanometers to about 500 nanometers.

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

11 . The all-solid secondary battery of claim 10 , wherein the plurality of particle has an average particle diameter of about 4 micrometers or less.

12 . The all-solid secondary battery of claim 10 ,

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 amorphous carbon, metal, or the metalloid, and are different.

13 . The all-solid secondary battery of claim 12 , 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.

14 . The all-solid secondary battery of claim 10 , 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.

15 . 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.

16 . The all-solid secondary battery of claim 15 , 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.

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 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.

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

19 . The all-solid secondary battery of claim 18 , 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.

20 . The all-solid secondary battery of claim 18 , 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.

21 . The all-solid secondary battery of claim 18 , wherein the sulfide solid electrolyte comprises at least one of Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —LiX wherein X is a halogen, Li 2 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 2 S—SiS 2 —LiBr, Li 2 S—SiS 2 —LiCl, Li 2 S—SiS 2 —B 2 S 3 —LiI, Li 2 S—SiS 2 —P 2 S 5 —LiI, Li 2 S—B 2 S 3 , Li 2 S—P 2 S 5 —Z m S n wherein m and n are each independently a positive number, and Z is Ge, Zn, or Ga, Li 2 S—GeS 2 , Li 2 S—SiS 2 —Li 3 PO 4 , Li 2 S—SiS 2 —Li p MO q wherein p and q are each independently a positive number, and M is at least one of P, Si, Ge, B, Al, Ga, or In, Li 7−x PS 6−x Cl x wherein 0≤x≤2, Li 7−x PS 6−x Br x wherein 0≤x≤2, or Li 7−x PS 6−x I x wherein 0≤x≤2.

22 . The all-solid secondary battery of claim 18 , wherein the sulfide solid electrolyte comprises an argyrodite-type solid electrolyte, and the argyrodite-type solid electrolyte comprises at least one of Li 7−x PS 6−x Cl x wherein 0≤x≤2, Li 7−x PS 6−x Br x wherein 0≤x≤2, or Li 7−x PS 6−x I x wherein 0≤x≤2.

23 . 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,

a third anode active material layer disposed between the anode current collector and the solid electrolyte layer, wherein the third anode active material layer comprises lithium or a lithium alloy,

wherein the first anode active material layer comprises

a first metal, and the first metal 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,

wherein the third anode active material layer is a plated layer,

wherein the first metal comprises indium,

wherein the second metal comprises at least one of silver, gold, platinum, palladium, silicon, aluminum, bismuth, magnesium, tin, or zinc,

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.

24 . An all-solid secondary battery of claim 23 , wherein the third anode active material layer consist of lithium.

25 . An all-solid secondary battery of claim 23 , wherein the third anode active material layer is 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.

26 . A method of manufacturing an all-solid secondary battery comprising:

providing a solid electrolyte layer;

disposing a first anode active material layer on a surface of the solid electrolyte layer, wherein the first anode active material layer comprises a first metal;

disposing a second anode active material layer on the first anode active material layer, wherein the second anode active material layer comprises a second metal; and

disposing a cathode active material layer on a surface of the solid electrolyte layer opposite the first anode active material layer to manufacture the all-solid secondary battery

wherein the first metal has a lithium-ion reduction potential greater than a reduction potential of the solid electrolyte, and

wherein a solid solubility of lithium in the second metal is greater than a solid solubility of lithium in the first metal,

wherein the first metal comprises indium,

wherein the second metal comprises at least one of silver, gold, platinum, palladium, silicon, aluminum, bismuth, magnesium, tin, or zinc,

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.

27 . A method of manufacturing an all-solid secondary battery comprising:

providing a solid electrolyte layer;

disposing a first anode active material layer on a surface of the solid electrolyte layer, wherein the first anode active material layer comprises a first metal;

disposing a second anode active material layer on the first anode active material layer, wherein the second anode active material layer comprises a second metal;

disposing a cathode active material layer on a surface of the solid electrolyte layer opposite the first anode active material layer;

plating a third anode active material layer by charging between the solid electrolyte layer and the first anode active material layer, or between the first anode active material layer and the second anode active material layer, or on a surface of the second anode active material layer not contacting the first anode active material to manufacture the all-solid secondary battery,

wherein the first metal has a lithium-ion reduction potential greater than a reduction potential of the solid electrolyte, and

wherein a solid solubility of lithium in the second metal is greater than a solid solubility of lithium in the first metal,

wherein the first metal comprises indium,

wherein the second metal comprises at least one of silver, gold, platinum, palladium, silicon, aluminum, bismuth, magnesium, tin, or zinc,

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.

28 . A protected electrode comprising:

a current collector;

a first layer;

a second layer disposed between the current collector and the first layer; and

a solid electrolyte,

wherein the first layer comprises a first metal, and the first metal has a lithium-ion reduction potential greater than a reduction potential of the solid electrolyte, and

wherein the second 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,

wherein the first metal comprises indium,

wherein the second metal comprises at least one of silver, gold, platinum, palladium, silicon, aluminum, bismuth, magnesium, tin, or zinc,

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.

29 . The protected electrode of claim 28 , further comprising lithium in the second layer.