Solid electrolyte, sodium all-solid secondary battery including the same, and its manufacturing method

Patent metadata

Field	Value
Publication number	US-2025201908-A1
Application number	US-202418769837-A
Country	US
Kind code	A1
Filing date	Jul 11, 2024
Priority date	Dec 19, 2023
Publication date	Jun 19, 2025
Grant date	—

Abstract

A sulfide solid electrolyte represented by Formula 1 and a sodium all-solid secondary battery including the same:Na3±xP1−(y1+y2)Wy1My2S4−zXz  Formula 1wherein in Formula 1, M may be a trivalent element, a tetravalent element, or a combination thereof, X is a halogen atom, or a combination thereof, 0≤x≤1, 0<y1≤50.5, 0≤z≤1, and 0≤y2≤0.5, wherein if z=0, y2 is not 0.

First claim

What is claimed is:

1 . A sulfide solid electrolyte represented by Formula 1:
Na 3±x P 1−(y1+y2) W y1 M y2 S 4−z X z   Formula 1
wherein in Formula 1, M is a trivalent element, a tetravalent element, or a combination thereof, X is a halogen atom, or a combination thereof, 0≤x≤1, 0<y1≤0.5, 0≤z≤1, and 0≤y2≤0.5, wherein if z=0, y2 is not 0.

2 . The solid electrolyte of claim 1 ,
wherein M is tin, silicon, aluminum, gallium, germanium, or a combination thereof.

3 . The solid electrolyte of claim 1 ,
wherein the solid electrolyte has a sodium ion conductivity at 25° C. of 0.05 millisiemens per centimeter or more.

4 . The solid electrolyte of claim 1 , wherein in Formula 1, 0.1≤y1≤0.3.

5 . The solid electrolyte of claim 1 , wherein in Formula 1, 0.01≤z≤0.5.

6 . The solid electrolyte of claim 1 , wherein the solid electrolyte comprises a compound represented by Formulas 2 to 4, or a combination thereof:
Na 3±x P 1−(y1+y2) W y1 Sn y2 S 4−z X z   Formula 2
wherein in Formula 2, 0≤x≤1, 0<y1<0.5, 0≤z≤1, and 0≤y2≤0.5, wherein if z=0, y2 is not 0, and X is a halogen atom,
Na 3±x P 1−(y1+y2) W y1 Al y2 S 4−z X z   Formula 3

wherein in Formula 3, 0≤x≤1, 0<y1 0.5, 0≤z≤1, and 0≤y2≤0.5, wherein if z=0, y2 is not 0, and X is a halogen atom,
Na 3±x P 1−(y1+y2) W y1 Sn y2 S 4−z X z   Formula 4

wherein in Formula 4, 0≤x≤1, 0<y1<0.5, 0≤z≤1, and 0≤y2≤0.5, wherein if z=0, y2 is not 0, and X is a halogen atom, and wherein X, x, y1, y2, and z in Formulas 2 to 4 are each independently selected.

7 . The solid electrolyte of claim 1 ,
wherein the solid electrolyte is Na 3 P 0.8 W 0.1 Si 0.1 S 4 , Na 3.1 P 0.8 W 0.1 Al 0.1 S 4 , Na 3 P 0.8 W 0.1 Sn 0.1 S 4 , Na 2.9 P 0.8 W 0.1 Si 0.1 S 3.9 Cl 0.1 , Na 3 P 0.8 W 0.1 Al 0.1 S 3.9 Cl 0.1 , Na 2.8 P 0.9 W 0.1 S 3.9 Cl 0.1 , Na 2.8 P 0.8 W 0.2 S 3.9 Cl 0.1 , Na 2.8 P 0.7 W 0.3 S 3.9 Cl 0.1 , Na 2.8 P 0.7 W 0.3 S 3.9 Cl 0.1 , Na 3 P 0.8 W 0.1 Sn 0.1 S 3.9 Cl 0.1 , Na 3 P 0.8 W 0.1 Si 0.05 Sn 0.05 S 4 , Na 2.9 P 0.8 W 0.1 Si 0.1 S 3.9 Cl 0.05 Br 0.05 , Na 3 P 0.8 W 0.1 Al 0.1 S 3.9 Cl 0.05 Br 0.05 , Na 2.8 P 0.9 W 0.1 S 3.9 Cl 0.05 Br 0.05 , Na 3 P 0.8 W 0.1 Ge 0.1 S 4 , Na 2.9 P 0.8 W 0.1 Ge 0.1 S 3.9 Cl 0.1 , Na 3.1 P 0.8 W 0.1 Ga 0.1 S 4 , Na 3 P 0.8 W 0.1 Ga 0.1 S 3.9 Cl 0.1 , Na 3 P 0.8 W 0.15 Si 0.05 S 4 , Na 3.1 P 0.8 W 0.15 Al 0.05 S 4 , Na 3 P 0.8 W 0.15 Sn 0.05 S 4 , Na 2.9 P 0.8 W 0.15 Si 0.05 S 3.9 Cl 0.1 , Na 2.9 P 0.8 W 0.15 Si 0.05 S 3.9 Cl 0.05 Br 0.05 , Na 3 P 0.8 W 0.15 Al 0.05 S 3.9 Cl 0.1 , Na 3 P 0.8 W 0.15 Al 0.05 S 3.9 Cl 0.05 Br 0.05 , Na 3 P 0.7 W 0.15 Si 0.15 S 4 , Na 3.1 P 0.7 W 0.15 Al 0.15 S 4 , Na 3 P 0.7 W 0.15 Sn 0.15 S 4 , Na 2.9 P 0.7 W 0.15 Si 0.15 S 3.9 Cl 0.1 , Na 3 P 0.7 W 0.15 Al 0.15 S 3.9 Cl 0.1 , or a combination thereof.

8 . The solid electrolyte of claim 1 , wherein the solid electrolyte comprises a glass-ceramic phase.

9 . The solid electrolyte of claim 9 , wherein a symmetric cell containing the solid electrolyte has an interfacial resistance of about 10 ohms to about 2,000 ohms.

10 . A sodium all-solid secondary battery comprising:
a cathode; an anode; and a solid electrolyte layer between the cathode and the anode, wherein the cathode comprises a cathode current collector and a cathode active material layer, and the anode comprises an anode current collector and an anode active material layer, wherein the cathode, the anode, the solid electrolyte layer, or a combination thereof comprise the solid electrolyte of claim 1 .

11 . The sodium all-solid secondary battery of claim 10 ,
wherein the anode active material layer comprises an anode active material and a binder.

12 . The sodium all-solid secondary battery of claim 11 ,
wherein the anode active material comprises a carbon-containing anode active material, a metal-containing anode active material, or a combination thereof.

13 . The sodium all-solid secondary battery of claim 12 ,
wherein the carbon-containing anode active material comprises amorphous carbon, crystalline carbon, porous carbon, or a combination thereof, and the metal-containing anode active material comprises gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or a combination thereof.

14 . The sodium all-solid secondary battery of claim 12 ,
wherein the anode active material comprises a mixture of first particles and second particles, wherein the first particles comprise amorphous carbon, and the second particles comprise a metal or a metalloid, wherein an amount of the second particles is about 1 weight percent to about 60 weight percent with respect to a total weight of the mixture.

15 . The sodium all-solid secondary battery of claim 11 , further comprising a metal layer between the anode current collector and the anode active material layer,
wherein the metal layer comprises sodium metal, a sodium alloy, or a combination thereof.

16 . The sodium all-solid secondary battery of claim 10 ,
wherein the cathode active material layer comprises one or more polyanionic compounds selected from Formulas 5 to 9, a layered sodium transition metal oxide represented by one of Formulas 10 and 11, a Prussian blue-type compound represented by Formula 12, or a combination thereof:
NaM(XO 4 )  Formula 5

wherein in Formula 5, M is manganese, iron, nickel, cobalt, chromium, copper, titanium, zinc, vanadium, zirconium, cerium, or a combination thereof, and X is phosphorus, sulfur, silicon, or a combination thereof,
Na x M y (XO 4 ) 3   Formula 6

wherein in Formula 6, 0<x≤3 and 0<y≤2, M is manganese, iron, nickel, cobalt, chromium, copper, titanium, zinc, vanadium, zirconium, cerium, or a combination thereof, and X is phosphorus, sulfur, silicon, or a combination thereof,
Na x M y (XO 4 )Z z   Formula 7

wherein in Formula 7, 0<x≤3, 0<y≤2, and 0<z≤1, M is manganese, iron, nickel, cobalt, chromium, copper, titanium, zinc, vanadium, zirconium, cerium, or a combination thereof, X is phosphorus, sulfur, silicon, or a combination thereof, and Z is F, Cl, Br, I, or a combination thereof,
Na x (MO a ) y (XO 4 ) z Z v   Formula 8

wherein in Formula 8, 0<x≤3, 0<y<2, 0<z≤2, 0<v≤1, and 0<a≤5, M is manganese, iron, nickel, cobalt, chromium, copper, titanium, zinc, vanadium, zirconium, cerium, or a combination thereof, X is phosphorus, sulfur, silicon, or a combination thereof, and Z is F, Cl, Br, I, or a combination thereof,
Na x M y (XO 4 ) z (Z 2 O 7 ) v   Formula 9

wherein in Formula 9, 0<x≤4, 0<y≤3, 0≤z≤3, and 0≤v≤2, M is manganese, iron, nickel, cobalt, chromium, copper, titanium, zinc, vanadium, zirconium, cerium, or a combination thereof, and X and Z are each independently phosphorus, sulfur, silicon, or a combination thereof,
Na x M1O 2   Formula 10

wherein in Formula 10, 0<x≤1, and M1 is titanium, vanadium, manganese, cobalt, nickel, iron, chromium, copper, or a combination thereof,
Na a Ni b M2 c M3 d M4 e M5 f O 2   Formula 11

wherein in Formula 11, 0.4≤a<1, 0<b<0.5, 0≤c<1, 0≤d<0.5, 0≤e<0.5, 0≤f<0.5, and 0<c+e, M2 is manganese, titanium, zirconium, or a combination thereof, M3 is magnesium, calcium, copper, zinc, cobalt, or a combination thereof, M4 is manganese, titanium, zirconium, or a combination thereof, and M5 is aluminum, iron, cobalt, molybdenum, chromium, vanadium, scandium, yttrium, or a combination thereof, or
Na x M1 y M2 z (CN) 6   Formula 12

wherein in Formula 12, 0<x≤2, 0<y<1, and 0<z<1, and M1 and M2 are each independently manganese, nickel, copper, cobalt, iron, zinc, vanadium, chromium, or a combination thereof.

17 . The sodium all-solid

Assignees

• Samsung Electronics Co Ltd

Inventors

• Lee Hyunpyo
• Ka Jonghoon
• Park Joungwon
• Kim Hyunjin
• Park Jungock
• Park Youngsin

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/58

  of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates · CPC title