Solid electrolyte for a negative electrode of a secondary battery including first and second solid electrolytes with different affinities for metal deposition electronchemical cell and method of manufacturing

Patent metadata

Field	Value
Publication number	US-10700377-B2
Application number	US-201815869743-A
Country	US
Kind code	B2
Filing date	Jan 12, 2018
Priority date	Jan 17, 2017
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

A solid electrolyte for a negative electrode of a secondary battery includes a first solid electrolyte having a first surface and a second solid electrolyte on the first solid electrolyte and having a second surface. The first solid electrolyte and the second solid electrolyte each have an ionic conductivity effective for a deposition metal, and the first surface and the second surface are different in composition, structure, or both. An electrode assembly and an electrochemical cell including the solid electrolyte and method for the manufacture thereof are also described.

First claim

What is claimed is:

1. A solid electrolyte for a negative electrode of a secondary battery, the solid electrolyte comprising:
a first solid electrolyte having a first surface; and
a second solid electrolyte on the first solid electrolyte, the second solid electrolyte having a second surface,
wherein the first solid electrolyte and the second solid electrolyte each have an ionic conductivity effective for a deposition metal,
wherein the first surface and the second surface are different in composition or composition and structure,
wherein a ratio of a length L 1 of the first solid electrolyte to a length L 2 of the second solid electrolyte is 0.1 to 1, and
wherein the solid electrolyte has a total length (L 1 +L 2 ) if 10 to 1,000 micrometers.

2. The solid electrolyte of claim 1 , further comprising an insulating frame surrounding one or both of the first and second solid electrolyte, wherein the insulating frame is non-porous.

3. The solid electrolyte of claim 1 , wherein the deposition metal comprises Li, Na, K, Mg, Zn, Ag, Al, or a combination thereof.

4. The solid electrolyte of claim 1 , wherein the deposition metal comprises Li, Na, Mg, or combination thereof.

5. The solid electrolyte of claim 1 , wherein the deposition metal is Li.

6. The solid electrolyte of claim 1 , wherein the first solid electrolyte and the second solid electrolyte are different in bulk composition, morphology, or both.

7. The solid electrolyte of claim 1 , wherein the first solid electrolyte and the second solid electrolyte each independently have an ionic conductivity for Li, Na, K, Mg, Zn, Ag, Al, or a combination thereof of at least 10 −3 S/m.

8. The solid electrolyte of claim 1 , wherein at least one of the first solid electrolyte or the second solid electrolyte is porous.

9. The solid electrolyte of claim 8 , wherein the first solid electrolyte and the second solid electrolyte comprise a void, wherein the void extends through the first solid electrolyte and the second solid electrolyte, and wherein the void is defined by the first surface of the first solid electrolyte and the second surface of the second solid electrolyte.

10. The solid electrolyte of claim 1 , wherein the first solid electrolyte and the second solid electrolyte each independently comprise a glass, a ceramic, a polymer, or a combination thereof.

11. The solid electrolyte of claim 10 , wherein the first solid electrolyte and the second solid electrolyte each independently comprise a ceramic comprising a lithium ceramic or a glass ceramic.

12. The solid electrolyte of claim 11 , wherein the lithium ceramic or glass ceramic comprises Li 7 La 3 Zr 2 O 12 ; Li 3 OX wherein X is Cl, Br, or I; Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 6 PS 5 Cl; Li 10 MP2S 12 wherein M is Ge, Si, or Sn; Li 3 PS 4 ; Li 7 P 3 S 11 ; Li 3 N; Li 2 S; LiBH 4 ; Li 3 BO 3 ; Li 2 S—P 2 S 5 ; Li 2 S—P 2 S 5 -L 4 SiO 4 ; Li 2 S—Ga 2 S 3 —GeS 2 ; Li 2 S—Sb 2 S 3 —GeS 2 ; Li 3.25 —Ge 0.25 —P 0.75 S 4 ; (La 1-x Li x )TiO 3 wherein 0<x<1; Li 6 La 2 CaTa 2 O 12 ; Li 6 La 2 ANb 2 O 12 wherein A comprises Ca, Sr, Ba; Li 6 La 3 Zr 1.5 WO 12 ; Li 6.5 La 3 Zr 1.5 TaO 12 ; Li 6.625 Al 0.25 La 3 Zr 2 O 12 ; Li 3 BO 2.5 N 0.5 ; Li 9 SiAlO 8 ; Li 1+x Al x Ge 2-x (PO 4 ) 3 ; Li 1+x Al x Ti 2-x (PO 4 ) 3 ; Li 1+x Ti 2-x Al x Si y (PO 4 ) 3-y wherein 0<x<1 and 0≤y<1; LiAl x Zr 2-x (PO 4 ) 3 ; LiTi x Zr 2-x (PO 4 ) 3 wherein 0<x<2, or a combination thereof.

13. The solid electrolyte of claim 11 , wherein the lithium ceramic or glass ceramic comprises
a garnet oxide of the formula L 5+x+2 y(D y La 3-y )(Me z Zr 2-z )O d , wherein L is a monovalent cation or a divalent cation, and provided that at least a part of or all of L is Li, wherein D is a monovalent or divalent cation, Me is one of a trivalent, tetravalent, pentavalent, and a hexavalent cation, 0<x+2y≤3, 0<y≤0.5, 0≤z<2, and 0<d≤12, optionally wherein O is partially or totally substituted with a pentavalent anion, a hexavalent anion, a heptavalent anion, or combination thereof;
an antiperovskite of the formula A 3 RX wherein A is Li or Na; X is Cl, Br, I, or a super halide, or a combination thereof; and R is O or S;
an oxide solid electrolyte of the formula Li 1+/−x M1 x M2 2-x (PO 4 ) 3 , wherein M1 is Al, Ga, In, Sc, Cr, Fe, Ta, or Nb; M2 is Ti, Zr, Hf, or Ge, and 0<x<1; or (La 1-x Li x )TiO 3 wherein 0<x<1;
a sulfide ceramic or glass electrolyte comprising Li 6 PS 5 X wherein X is Cl, Br, or I; Li 10 MP 2 S 12 wherein M is Ge, Si, or Sn; Li 2 S—P 2 S 5 ; Li 2 S—P 2 S 5 -L 4 SiO 4 ; Li 2 S—Ga 2 S 3 —GeS 2 ; Li 2 S—Sb 2 S 3 —GeS 2 ; Li 3.25 —Ge 0.25 —P 0.75 S 4 ; Li 3 PS 4 ; Li 7 P 3 S 11 ; Li 3 N; Li 2 S; LiBH 4 ; or Li 3 BO 3 ;
or a combination thereof.

14. The solid electrolyte of claim 1 , wherein the first surface has a first surface energy towards the deposition metal and the second surface has a second surface energy towards the deposition metal, and wherein the first surface energy is greater than the second surface energy.

15. The solid electrolyte of claim 1 , wherein the first surface has a composition that is different from a bulk composition of the first solid electrolyte, the second surface has a composition that is different from a bulk composition of the second solid electrolyte, or the first surface has a composition that is different from a bulk composition of the first solid electrolyte and the second surface has a composition that is different from a bulk composition of the second solid electrolyte.

16. The solid electrolyte of claim 1 ,
wherein the first surface has a first surface energy towards the deposition metal and the second surface has a second surface energy towards the deposition metal, and wherein the first surface energy is greater than the second surface energy, and
wherein the first surface has a first charge transfer resistance for deposition of the deposition metal and the second surface has a second charge transfer resistance for deposition of the deposition metal, and wherein the first charge transfer resistance is greater than the second charge transfer resistance.

17. The solid electrolyte of claim 1 , wherein an area of the first surface is less than or equal to an area of the second surface.

18. The solid electrolyte of claim 17 , wherein a ratio of the area of the first surface to the area of the second surface is 0.1 to 1.

19. The solid electrolyte of claim 1 , wherein the first surface has a first charge transfer resistance for deposition of the deposition metal and the second surface has a second charge transfer resistance for deposition of the deposition metal, and wherein the first charge transfer resistance is greater than the second charge transfer resistance.

20. The solid electrolyte of claim 19 , wherein a ratio of the first charge transfer resistance to the second charge transfer resistance is greater than 30.

21. The solid electrolyte of claim 1 , wherein the first surface and the second surface each independently further comprise a carbonate, a halogen, an oxide, a polymer, a silicide, a phosphide, a sulfide, a metal of Groups 2 to 16, or a combination thereof.

22. The solid electrolyte of claim 21 , wherein the first surface comprises the carbonate, the halogen, the oxide, the polymer, or combination thereof in a first amount, the second surface comprises the oxide, the carbonate, the silicide, the phosphide, the sulfide, the aluminum oxide, the magnesium, the niobium, the gold, the silver, the calcium, the indium, the tin, the antimony, the zinc, the poly

Assignees

• Samsung Electronics Co Ltd
• Corning Inc

Inventors

• Thomas-Alyea Karen E
• Lee Yong-Gun
• Miara Lincoln
• Kim Hyunseok
• Kim Jusik
• Badding Michael E
• Song Zhen

Classifications

• H01M2300/0074

  Ion conductive at high temperature · CPC title

• H01M2300/0068

  inorganic · CPC title

• H01M10/39

  working at high temperature · CPC title

• H01M10/0565

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M10/0562

  Solid materials · CPC title