Sodium all-solid secondary battery

Patent metadata

Field	Value
Publication number	US-2025087743-A1
Application number	US-202418427499-A
Country	US
Kind code	A1
Filing date	Jan 30, 2024
Priority date	Sep 8, 2023
Publication date	Mar 13, 2025
Grant date	—

Abstract

A sodium all-solid secondary battery including: a cathode; an anode; a sulfide-containing electrolyte between the cathode and the anode; an oxide-containing electrolyte between the sulfide-containing electrolyte and the anode; and a first bonding layer between the oxide-containing electrolyte and the sulfide-containing electrolyte, wherein the cathode includes a cathode current collector and a cathode active material layer, the anode includes an anode current collector and an anode active material layer, and the first bonding layer includes a metal capable of forming an alloy with sodium, a sodium ion-conductive material, or a combination thereof.

First claim

What is claimed is:

1 . A sodium all-solid secondary battery comprising:
a cathode; an anode; a sulfide-containing electrolyte between the cathode and the anode; an oxide-containing electrolyte between the sulfide-containing electrolyte and the anode; and a first bonding layer between the oxide-containing electrolyte and the sulfide-containing electrolyte, wherein the cathode comprises a cathode current collector and a cathode active material layer, the anode comprises an anode current collector and an anode active material layer, and the first bonding layer comprises a metal capable of forming an alloy with sodium, a sodium ion-conductive material, or a combination thereof.

2 . The sodium all-solid secondary battery of claim 1 , wherein the metal capable of forming an alloy with sodium comprises a first metal, and
the first metal comprises gold, tin, titanium, zinc, platinum, silicon, silver, bismuth, germanium, lead, antimony, or a combination thereof.

3 . The sodium all-solid secondary battery of claim 1 , wherein a thickness of the first bonding layer is less than a thickness of the sulfide-containing solid electrolyte, a thickness of the oxide-containing solid electrolyte, or both.

4 . The sodium all-solid secondary battery of claim 1 , wherein the first bonding layer has a Mohs hardness of less than about 4.

5 . The sodium all-solid secondary battery of claim 1 , wherein the sodium ion-conductive material comprises a solid electrolyte, a gel electrolyte, a liquid electrolyte, an ionic liquid, or a combination thereof,
the solid electrolyte comprises a sulfide-containing solid electrolyte, an oxide-containing solid electrolyte, a polymer solid electrolyte, or a combination thereof, and the gel electrolyte comprises a polymer gel electrolyte.

6 . The sodium all-solid secondary battery of claim 1 , wherein the sulfide-containing solid electrolyte comprises Na 3 PS 4 , Na 3-x PS 4-x Cl x wherein 0<x<3,
Na 3−x P 1−x W x S 4 wherein 0≤x<1, Na 3 PS 4−x O x wherein 0<x<4, Na 3−2x Ca x PS 4 wherein 0<x<1.5, Na 3 SbS 4 , Na 3−x Sb 1−x W x S 4 wherein 0≤x<1, Na 2.88 Sb 0.88 W 0.12 S 4−x NaI wherein 0<x<1, Na 3 W x Si x Sb 1−2x S 4 wherein 0≤x<0.5, Na 3−x Sb 1−x W x S 4−3x O 3x wherein 0≤x<1, Na 3 SbS 4 —Na 2 W x S 4 I 6x−4 wherein 0≤x<1, Na 2 S—P 2 S 5 , Na 2 S—P 2 S 5 —NaX wherein X is F, Cl, Br, I, or a combination thereof, Na 2 S—P 2 S 5 —Na 2 O, Na 2 S—P 2 S 5 —Na 2 O—NaI, Na 2 S—SiS 2 , Na 2 S—SiS 2 —NaI, Na 2 S—SiS 2 —NaBr, Na 2 S—SiS 2 —NaCl, Na 2 S—SiS 2 —B 2 S 3 —NaI, Na 2 S—SiS 2 —P 2 S 5 —NaI, Na 2 S—B 2 S 3 , Na 2 S—P 2 S 5 —Z m S n , wherein 0<m≤10, 0<n≤10, and Z is Ge, Zn, Ga, or a combination thereof, Na 2 S—GeS 2 , Na 2 S—SiS 2 —Na 3 PO 4 , Na 2 S—SiS 2 -Na p MO q wherein 0<p≤10, 0<q≤10, and M is P, Si, Ge, B, Al, Ga, In, or a combination thereof, Na 7−x PS 6−x Cl x wherein 0≤x≤2, Na 7−x PS 6−x Br x wherein 0≤x≤2, Na 7−x PS 6−x I x wherein 0≤x≤2, Na 10 MP 2 S 12 wherein M is Ge, Si, S n , or a combination thereof, or a combination thereof, and the sulfide-containing solid electrolyte is crystalline, amorphous, glassy, or glass ceramic.

7 . The sodium all-solid secondary battery of claim 1 , wherein the oxide-containing solid electrolyte comprises Na a M1 b M2 c O d , wherein M1 is Al, Y, Yb, Nd, Nb, Ti, or Hf, M2 is Si or P, 1≤a≤6 1≤b≤3, 2≤c≤5, and 5≤d≤15, Na 1+x Zr 2 Si x P 3−x O 12 wherein 0≤x≤3, Na x M 2 (PO 4 ) 3 wherein M is V or Ti, and 0≤x≤3, Na 3+x La (2/3−x)(1/3−2x) TiO 3 wherein 0.04<x<0.16, Na 1+x Al x Ti 2−x (PO 4 ) 3 wherein 0<x<2, Na 1+x Al x Ge 2−x (PO 4 ) 3 wherein 0<x<2, Na 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 p Ti 1−p )O 3 wherein 0≤p≤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 , Na 3 PO 4 , Na x Ti y (PO 4 ) 3 wherein 0<x<2 and 0<y<3, Na x Al y Ti z (PO 4 ) 3 wherein 0<x<2, 0<y<1, and 0<z<3, Na 1+x+y (Al p Ga 1−p ) x (Ti q Ge 1−q ) 2−x Si y P 3−y O 12 wherein 0≤x≤1, 0≤y≤1, 0<p≤1, and 0<q≤1, Na x La y TiO 3 wherein 0<x<2 and 0<y<3, Na 2 O, NaOH, Na 2 CO 3 , NaAlO 2 , Na 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 , Na 3+x La 3 M 2 O 12 wherein M is Te, Nb or Zr, and 1≤x≤10, Na 7 La 3 Zr 2 O 12 , Na 3+x La 3 Zr 2-a M a O 12 , wherein M is Ga, W, Nb, Ta, or Al, 0<a<2, and 1≤x≤10, or a combination thereof, and
the oxide-containing solid electrolyte is crystalline, amorphous, glassy, or glass ceramic.

8 . The sodium all-solid secondary battery of claim 1 , wherein the cathode active material layer comprises a polyanionic compound represented by Formulae 1 to 5, a layered sodium transition metal oxide represented by Formulae 6 and 7, or a Prussian blue compound represented by Formula 8:
NaM1(XO 4 )  Formula 1
wherein in Formula 1, M1 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 M2 y (XO 4 ) 3   Formula 2

wherein in Formula 2, 0<x≤3, 0<y≤2, M2 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 M3 y (XO 4 )Z z   Formula 3

wherein in Formula 3, 0<x≤3, 0<y≤2, 0<z≤1, M3 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 (M4O a ) y (XO 4 ) z Z v   Formula 4

wherein in Formula 4, 0<x≤3, 0<y≤2, 0<z≤2, 0<v≤1, 0<a≤5, M4 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 M5 y (XO 4 ) z (Z 2 O 7 ) v   Formula 5

wherein in Formula 5, 0<x≤4, 0<y≤3, 0≤z≤3, 0≤v≤2, M5 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 M6O 2   Formula 6

wherein in Formula 6, 0<x≤1, and M6 is titanium, vanadium, manganese, cobalt, nickel, iron, chromium, copper, or a combination thereof,
Na a Ni b M7 c M8 d M9 e M10 f O 2   Formula 7

wherein in Formula 7, 0.4≤a<1, 0<b<0.5, 0≤c<1, 0≤d<0.5, 0≤e<0.5, 0≤f<0.5, 0<c+e<1.5, M7 is manganese, titanium, zirconium, or a combination thereof, M8 is magnesium, calcium, copper, zinc, cobalt, or a combination thereof, M9 is manganese, titanium, zirconium, or a combination thereof, and M10 is aluminum, iron, cobalt, molybdenum, chromium, vanadium, scandium, yttrium, or a combination thereof, and
Na x M11 y M12 z (CN) 6   Formula 8

wherein in Formula 8, 0<x≤2, 0<y≤1, 0<z≤1, and M12 and M12 are each independently manganese, nickel, copper, cobalt, iron, zinc, vanadium, chromium, or a combination thereof.

9 . The sodium all-solid secondary battery of claim 1 , further comprising a second bonding layer between the cathode and the sulfide-containing electrolyte, wherein the second bonding layer comprises a second metal, and the second metal comprises gold, tin, titanium, zinc, platinum, silicon, silver, bismuth, germanium, lead, antimony, or a combination thereof.

10 . The sodium all-solid secondary battery of claim 1 , wherein the anode active material layer comprises an anode active material and a binder, and
the anode active material comprises a carbonaceous anode active material, a metallic anode active material, or a combination thereof.

Assignees

• Samsung Electronics Co Ltd

Inventors

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

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M4/381

  Alkaline or alkaline earth metals elements (H01M4/40 takes precedence) · CPC title